A World CompendiumThe Pesticide Manual Sixteenth Edition Supplementary Entries – Extended Editor: C. MacBean Promoting the science and practice of sustainable crop production © 2012 BCPC (British Crop Production Council) All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission of the copyright owner. British Library Cataloguing in Publication Data. A catalogue record of this book is available from the British Library. ISBN 978 1 901396 86 7 First published 1968 Seventh edition 1983 Thirteenth edition 2003 Second edition 1971 Eighth edition 1987 Fourteenth edition 2006 Third edition 1972 Ninth edition 1991 Fifteenth edition 2009 Fourth edition 1974 Tenth edition* 1994 Fifth edition 1977 Eleventh edition 1997 Sixth edition 1979 Twelfth edition 2000 * The tenth edition incorporated The Agrochemicals Handbook, previously published by The Royal Society of Chemistry. Published by: BCPC, 7 Omni Business Centre, Omega Park, Alton, Hampshire, GU34 2QD, UK Tel +44 (0) 1420 593 200 Fax +44 (0) 1420 593 209 www.bcpc.org All BCPC publications can be purchased from: BCPC Publications, 7 Omni Business Centre, Omega Park, Alton, Hampshire, GU34 2QD, UK Tel +44 (0) 1420 593 200 Fax +44 (0) 1420 593 209 Email:
[email protected] Or direct from the BCPC Shop at www.bcpc.org/shop Disclaimer: Every effort has been made to ensure that all information in this edition of The Pesticide Manual is correct at the time of going to press. However, the editor and the publisher do not accept liability for any error or omission in the content, or for any loss, damage or any other accident arising from the use of the products listed therein. Before handling, storing or using any approved crop protection product, it is essential to follow the instructions on the label. iii Supplementary Entries These entries include (i) superseded materials, believed to be no longer manufactured, or marketed, for crop protection use; (ii) some materials that are in the public domain and believed to be in late stages of development; and (iii) materials that reached late development but were ultimately not marketed. These entries are short descriptions. For chemical materials, they may include the following information: Sequential entry number. A header name, with an indication of the type of name (such as common name, chemical name, etc.). Chemical Abstracts Service Registry Number (CAS RN). Approved common name (if different from the name in the header, or if other common names have been approved by national bodies). Molecular formula (M.f.). Other names. Code numbers (development codes). The main former product or products. For an explanation of this information see the Guide to Using the Main Entries, p. viii of The Pesticide Manual Sixteenth Edition. It is diffcult, in some cases, to be sure whether or not all commercial activity in a substance has ceased; some of these ‘superseded’ materials are known to be still in use for non-agricultural purposes. The Editor will be grateful for details of any materials in this section that are still in commercial, agricultural use; he can be contacted via the publishers, or at
[email protected]. Supplementary Entries – Extended AC 94,377 1 AC 94,377 Plant growth regulator NOMENCLATURE: IUPAC name 1-(4-chloro-1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)cyclohexane-1- carboxamide; 1-phthalimidocyclohexane-1-carboxamide Chemical Abstracts name 1-(4-chloro-1,3-dihydro-1,3-dioxo-[2H]-isoindol-2-yl)- cyclohexanecarboxamide CAS RN [51971–67–6] Development codes AC 94,377; CL 94,377 (both Cyanamid) Smiles code NC(=O)C1(CCCCC1)N 2 C(=O)c3cccc(Cl)c3C2=O PHYSICAL CHEMISTRY: Mol. wt. 306.7 M.f. C 15 H 15 ClN 2 O 3 Form White crystalline solid. M.p. 193–195 °C Solubility In water 30 ppm (25 °C). In acetone <2%, N-methylpyrrolidone 35%, dichloromethane <2%, DMSO >20% (all 20 °C). COMMERCIALISATION: History Evaluated by American Cyanamid Co. APPLICATIONS: Biochemistry Not known. Activity mimics that of gibberellic acid in various phytohormone bioassays (J. C. Suttle & J. F. Hultstrand, Plant Physiology, 80 (5), 115 (1986)). Uses Growth promoter, increasing the stem number, stem length and commercial acceptability of cut stems in hybrid tea roses. Benefcial effects have been reported in other crops. Formulation types SC. PRODUCTS: Discontinued products ‘Surestem’* (BASF). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male and female rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for male and female rabbits >2000 mg/kg. Mildly irritating to eyes; non-irritating to skin (male rabbits). Other Non-mutagenic in the Ames test, microbial mutagenicity assay, and host-mediated assay. Details PM12, Entry 3. N Cl O O NH 2 O 2 The Pesticide Manual Sixteenth Edition © BCPC 2012 acetic acid ACD 10614; ACD 10435 Herbicide NOMENCLATURE: IUPAC name 1,1,1,7,7,7-hexafuoro-4-methyl-2,6-bis(trifuoromethyl)hept-3-ene-2,6-diol (i) and tautomer 1,1,1,7,7,7-hexafuoro-4-methylene-2,6-bis(trifuoromethyl)heptane-2,6- diol (ii); forming monosodium 1,1,1,7,7,7-hexafuoro-4-methyl-2,6-bis(trifuoromethyl) hept-3-ene-2,6-diolate and monosodium 1,1,1,7,7,7-hexafuoro-4-methylene-2,6- bis(trifuoromethyl)heptane-2,6-diolate Chemical Abstracts name 1,1,1,7,7,7-hexafuoro-4-methyl-2,6-bis(trifuoromethyl)-3- heptene-2,6-diol (i) and 1,1,1,7,7,7-hexafuoro-4-methylene-2,6-bis(trifuoromethyl)-2,6- heptanediol (ii) CAS RN [756–91–2] (i); [16202–91–8] (ii); [19493–94–8] monosodium salts Development codes ACD 10 614 (i + ii); ACD 10 435 (monosodium salts) PHYSICAL CHEMISTRY: Mol. wt. 388.2 M.f. C 10 H 8 F 12 O 2 Form Monosodium salts form a colourless solid. M.p. 143–145 °C; monosodium salts >300 °C Solubility Practically insoluble in water, benzene, dichloromethane, xylene; soluble in alkali, acetone, diethyl ether, DMF, DMSO, dioxane, bis(2-methoxyethyl) ether. Sodium salt soluble in water, acetone, diethyl ether, dioxane, ethanol; insoluble in benzene, hexane. COMMERCIALISATION: History Herbicide evaluated by Allied Chemical Corp., Agrochemical Division (later Hopkins Agricultural Chemical Co.). APPLICATIONS: Mode of action Selective herbicide. Uses Both the diol and its monosodium salt pre-em. at 2.3–6.8 kg/ha controlled weeds selectively in cereals, maize, sorghum and soya beans; and post-em. at 2.3 kg/ha in maize, sorghum, soya beans and wheat. Formulation types EC (diol); GR (diol); SP (hydrated sodium salt); WP (diol). MAMMALIAN TOXICOLOGY: Oral Diol: Acute oral LD 50 for fasted albino rats 17.8 mg/kg. Monosodium salt: 20.2 mg/kg. Skin and eye Acute percutaneous LD 50 for albino rabbits 141 mg/kg. Details PM4, p. 296. acetic acid Herbicide See also The Manual of Biocontrol Agents 4th edn entry: 2:151 NOMENCLATURE: CAS RN [64–19–7] PRODUCTS: Other products ‘Nature’s Glory Weed & Grass Killer’ (Ecoval). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Rev. Rep. SANCO/2602/08 (2008) EU Status (1107/2009) 2008/127/EC Supplementary Entries – Extended acrylonitrile 3 acetoprole Acaricide, insecticide, nematicide NOMENCLATURE: Common name (m) acé(toprole) (F-ISO); acetoprole (BSI, E-ISO) IUPAC name (±)-1-[5-amino-1-(2,6-dichloro-α,α,α-trifuoro-p-tolyl)-4-(methylsulfnyl) pyrazol-3-yl]ethanone Chemical Abstracts name 1-[5-amino-1-[2,6-dichloro-4-(trifuoromethyl) phenyl]-4-(methylsulfnyl)-1H-pyrazol-3-yl]ethanone CAS RN [209861–58–5] Development codes RPA 115782 PHYSICAL CHEMISTRY: Mol. wt. 400.2 M.f. C 13 H 10 Cl 2 F 3 N 3 O 2 S COMMERCIALISATION: Manufacturers Rhône-Poulenc acrylonitrile Insecticide NOMENCLATURE: Common name acrylonitrile (BSI, E-ISO, F-ISO, ESA, accepted in lieu of a common name) IUPAC name acrylonitrile Chemical Abstracts name 2-propenenitrile Other names vinyl cyanide CAS RN [107–13–1] EC no 203–466–5 Smiles code C=CC#N PHYSICAL CHEMISTRY: Mol. wt. 53.06 M.f. C 3 H 3 N M.p. –82 °C B.p. 77 °C V.p. 1.37 × 107 mPa (25 °C) S.g./density 0.801 (4–25 °C); gaseous, 1.83 (air = 1) Solubility In water ca. 8% (room temperature). Unlimited miscibility with common organic solvents. Stability Readily polymerised, sometimes explosively. Addition of stabilizers is necessary. F.p. 0 °C. Mixtures with air having 3–17% vol./vol. acrylonitrile are fammable. COMMERCIALISATION: History Developed as a fumigant insecticide (The Chemistry of Acrylonitrile) by American Cyanamid Co. APPLICATIONS: Biochemistry Respiratory action similar to that of hydrogen cyanide. Mode of action Fumigant insecticide Uses Fumigant insecticide (ca. 5–10 g/m 3 ) for the control of pests in living areas and warehouses, machines in milling, baking, and food processing. Formulation types TC. PRODUCTS: Discontinued products ‘VCN’* (Stauffer); ‘Ventox’* (Detia Degesch). ANALYSIS: In air, by absorption of the fumes in a measured quantity of air in an alkaline solution of laurylmercaptan in isopropanol; the mercaptan is introduced at the double bond. Oxidation of excess mercaptan to the disulfde with iodine solution and back-titration of the unused 4 The Pesticide Manual Sixteenth Edition © BCPC 2012 afdopyropen iodine or electrophotometric determination (J. Haslam & G. Newlands Analyst, 1955, 80, 50). Residues: cyanogen bromide, formed by the action of bromine (in uv light) on acrylonitrile generated in a nitrogen stream, forms a dye with benzidine-pyridine which can be determined colorimetrically (Man. Pestic. Residue Anal., 120). For gc determination see Anal. Methods Pestic. Plant Growth Regul. 1972, 6, 259–260. For spectrophotometric determination of the pyridine-acrylonitrile complex see M. E. Hall & J. W. Stevens (Anal. Chem. 1977, 49, 2277–2279). Methods reviewed by J. L. Daft in Comp. Anal. Profles, Chapter 11. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 28 (1983). JMPR Evaln. 5 (1965). HSG 1 (1986). ICSC 0092 (2001). CICAD 39 (2002). IARC 71 (1999). MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 93 mg/kg. Skin and eye Liquid acrylonitrile permeates through the skin. Inhalation Exposure to air containing 635 and 110 ml/m 3 is lethal to rats and dogs, respectively, within 4 hours. ADI/RfD (JMPR) No ADI [1965]; (EPA) RfD 0.01 mg/kg b.w. [1993]. Other It may be a carcinogen. Toxicity Class WHO (a.i.) FM. EC Classifcation F; R11| R45| T; R23/24/25| Xi; R37/38, R41| R43| N; R51, R53| concn. dep. ECOTOXICOLOGY: Bees Toxicity to bees not signifcant. Details PM5, p. 3. afdopyropen Insecticide NOMENCLATURE: Common name afdopyropen (pa ISO) IUPAC name [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-(cyclopropylcarbonyloxy)- O O N O HO O O CH 3 H 2 C H 3 C O O H CH 3 H OH Supplementary Entries – Extended AKH-7088 5 1,2,3,4,4a,5,6,6a,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-py- ridyl)-11H,12H-benzo[f]pyrano[4,3-b]chromen-4-yl]methyl cyclopropanecarboxylate Chemical Abstracts name [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl) oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl- 11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl cyclopropanecarboxylate CAS RN [915972–17–7] Development codes ME5343 Smiles code O=C(OC(C1=CN=CC=C1)=C2)C3=C2O[C@@]([C@@H](O)C4)(C) [C@@]([C@H]3O)([H])[C@]5(C)[C@@]4([H])[C@](C)(COC(C6CC6)=O)[C@@H] (OC(C7CC7)=O)CC5 PHYSICAL CHEMISTRY: Mol. wt. 593.7 M.f. C 33 H 39 NO 9 AKH-7088 Herbicide NOMENCLATURE: IUPAC name methyl (EZ)-1-[5-(2-chloro-α,α,α-trifuoro-p-tolyloxy)-2-nitrophenyl]-2- methoxyethylideneamino-oxyacetate Chemical Abstracts name methyl [[[1-[5-[2-chloro-4-(trifuoromethyl)phenoxy]- 2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate CAS RN [104459–82–7] Development codes AKH-7088 Smiles code COCC(=NOCC(=O)OC) c1cc(Oc2ccc(cc2Cl)C(F)(F)F)ccc1[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 476.8 M.f. C 19 H 16 ClF 3 N 2 O 7 Form Colourless crystals. M.p. 57.7–58.1 °C Solubility In water 1 mg/l (20 °C). In dichloromethane >50%, toluene 15% (both 20 °C). COMMERCIALISATION: History Discovered in 1984 by Asahi Chemical Industry Co. Ltd. Reported by Y. Hayashi et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1989, 1, 53–58). APPLICATIONS: Biochemistry (E)- and (Z)- isomers show similar biological activity. Uses Post-emergence control of broad-leaved weeds, including velvetleaf, cockleburs, and Jimson weed, in soya beans, at 0.1–0.2 kg/ha. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 2000 mg/kg. Moderate skin irritation; non-irritating to eyes (male rabbits). Other Non- mutagenic in the Ames test. F 3 C Cl O NO 2 C CH 2 OCH 3 NOCH 2 CO 2 CH 3 6 The Pesticide Manual Sixteenth Edition © BCPC 2012 aldimorph Details PM12, Entry 15. aldimorph Fungicide FRAC 5, G2; SBI class II, amine: morpholine NOMENCLATURE: Common name aldimorphe ((m) F-ISO); aldimorph (BSI, E-ISO) IUPAC name 4-alkyl-2,5 (or 2,6) -dimethylmorpholine, mixed compounds where the alkyl substituent may be octyl, decyl, dodecyl, tetradecyl or hexadecyl and where the main component is 4-dodecyl-2,6-dimethylmorpholine Chemical Abstracts name aldimorph CAS RN [91315–15–0] Development codes B 8243 PHYSICAL CHEMISTRY: Mol. wt. 283.5 M.f. C 18 H 37 NO (main component) Form Colourless liquid. M.p. –27 to –19 °C B.p. 110–140 °C /0.1 mbar V.p. 5.5 × 10 –1 mPa (21.8 °C) Solubility In water c. 20 mg/l (25 °C). Stability Very stable between pH 3 and pH 10. Stable to light. On heating abovec. 60 °C, gives a weak brown coloration. COMMERCIALISATION: Manufacturers Hermania APPLICATIONS: Biochemistry Ergosterol biosynthesis inhibitor, by inhibition of sterol reduction (sterol- Δ 14 -reductase) and isomerisation (Δ 8 to Δ 7 -isomerase). Mode of action Systemic, long-term, also curative action. Absorbed through leaves and roots. Inhibits formation of haustoria in Erysiphe graminis. Uses Controls mildew on spring and winter barley. Formulation types EC. PRODUCTS: Discontinued products ‘Falimorph’* (Fahlberg-List). ANALYSIS: Product analysis by acidimetric titration in non-aqueous medium. Residues by extraction wth methanol, transfer to hexane, column chromatographic clean-up on aluminium oxide, and colorimetric determination at 540 nm of coloured substances released by hydrochloric acid from the methyl orange-active ingredient salt. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >3000 mice 9700 mg/kg. Skin and eye Dermal LD 50 for guinea pigs 1430 mg/kg. Skin irritant. NOEL In 90 d feeding trials on rats, highest dose without activity was 2 mg/kg b.w. daily. ADI/RfD (BfR) 0.01 mg/kg b.w. [1991] Other Possible teratogen. Supplementary Entries – Extended aldoxycarb 7 ECOTOXICOLOGY: Fish LC 50 (96 h) for carp 2.83, salmon 0.38 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Plants The a.i. content in barley and wheat decreases from 18 mg/kg at application to 0.14 mg/kg after 30 d and 0.1 mg/kg after 45 and 57 d. aldoxycarb Acaricide, insecticide, nematicide IRAC 1A NOMENCLATURE: Common name aldoxycarb (BSI, E-ISO, ANSI, ESA); aldoxycarbe ((m) F-ISO) IUPAC name 2-mesyl-2-methylpropionaldehyde O-methylcarbamoyloxime; 2-methyl-2- methylsulfonylpropionaldehyde O-methylcarbamoyloxime Chemical Abstracts name 2-methyl-2-(methylsulfonyl)propanal O-[(methylamino) carbonyl]oxime Other names aldicarb sulfone; sulfocarb CAS RN [1646–88–4] Development codes UC 21 865 Smiles code CNC(=O)ON=CC(C)(C)S(=O)(=O)C PHYSICAL CHEMISTRY: Mol. wt. 222.3 M.f. C 7 H 14 N 2 O 4 S Form White crystalline powder with a sulfurous odour. M.p. 140–142 °C V.p. 12 mPa (25 °C) Henry 2.67 × 10 –4 Pa m 3 mol –1 (calc.) Solubility In water c. 10 g/l (25 °C). In chloroform 32, acetonitrile 74, methanol 30, dichloromethane 41, acetone 50 (all in g/l). Stability Stable, but decomposition occurs above 140 °C. Rapidly hydrolysed in acidic or alkaline media. COMMERCIALISATION: History Insecticide and nematicide reported by M. H. J. Weiden et al. (J. Econ. Entomol., 1965, 58, 154). Introduced by Union Carbide Corp. (later Rhône-Poulenc Agrochimie). Patents US 3217037 Manufacturers Rhône-Poulenc APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic; taken up through roots. Uses Control of aphids, thrips, mites, nematodes, leafhoppers and other pests on cotton, tobacco, peanuts, maize, potatoes, cole crops and vegetables. Could be applied as a soil treatment, foliar spray, seed dressing or transplant water treatment. Phytotoxicity Soya beans and french bean seedlings are not tolerant. Formulation types WP; GR; SC; FS. Compatibility Not fully known, but has been found to be compatible with most common herbicides, insecticides, nematicides and fungicides used on tobacco. PRODUCTS: Discontinued products ‘Standak’* (Rhône-Poulenc). CH C CH 3 CH 3 N O C NHCH 3 O CH 3 SO 2 8 The Pesticide Manual Sixteenth Edition © BCPC 2012 aldrin ANALYSIS: Product analysis by i.r. spectrometry (CIPAC Handbook, 1980, 1A, 1094). Residues determined by glc with FPD (R. T. Krause, J. Assoc. Offc. Anal. Chem., 1980, 63, 1114; R. R. Romine, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 147; J. H. Smelt et al., loc. cit.). In drinking water by rplc and fuorimetry of liberated methylamine (Environ. Chem. Methods). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986); a review of carbamate pesticides in general. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 21.4 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 1000, rabbits 200 mg/kg. No skin or eye irritation in standard tests. Inhalation LC 50 (4 h) for rats 0.14 mg/l air (dust). NOEL In life-span feeding trials, NOEL for mice 9.6, rats 2.4 mg/kg. ADI/RfD (EPA) 0.001 mg/kg b.w. [1993]. Other No teratogenic, reproductive or mutagenic effects observed. Toxicity Class WHO (a.i.) Ib EPA (formulation) I ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks 33.5 mg/kg. Dietary LC 50 (5 d) for mallard ducks >10 000 mg/kg diet, bobwhite quail 5706 mg/kg diet. Fish LC 50 (96 h) for trout 40, bluegill sunfsh 55.5 mg/l. Bees Low toxicity to bees. ENVIRONMENTAL FATE: Animals Degradation in animals is by hydrolysis of the carbamate ester to aldoxycarb oxime, and elimination of the methylcarbamate group to give aldoxycarb nitrile. Plants Degradation in plants is the same as in animals. Soil/Environment See aldicarb. Details PM10, Entry 18. aldrin Insecticide IRAC 2A NOMENCLATURE: Common name HHDN (for pure material) (BSI, E-ISO, F-ISO, JMAF; exception USA); aldrin (for material containing 95% HHDN) (BSI, E-ISO, ESA, JMAF); aldrine (for material containing 95% HHDN) ((m) F-ISO) IUPAC name (1R,4S,4aS,5S,8R,8aR)-1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro- 1,4:5,8-dimethanonaphthalene; 1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-exo-1,4- endo-5,8-dimethanonaphthalene Chemical Abstracts name (1α,4α,4aβ,5α,8α,8aβ)-1,2,3,4,10,10-hexachloro- 1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene CAS RN [309–00–2] Cl Cl Cl Cl Cl Cl Supplementary Entries – Extended aldrin 9 EC no 206–215–8 Development codes Compound 118 (Hyman) Smiles code ClC1=C(Cl)C2(Cl)C3C4CC(C=C4)C3C1(Cl)C2(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 364.9 M.f. C 12 H 8 Cl 6 Form Pure HHDN is a colourless crystalline solid; aldrin is a tan to dark brown waxy solid. M.p. 104–104.5 °C (HHDN); (aldrin 49–60 °C) B.p. 145 °C /2 mmHg V.p. 8.6 mPa (20 °C) Solubility In water 0.027 mg/l (27 °C). In acetone, benzene and xylene >600 g/l (27 °C). Stability Thermally stable up to 200 °C. Stable between pH 4 and 8. Reacts with concentrated acids and phenols in the presence of oxidising agents to give dieldrin. COMMERCIALISATION: History Insecticide reported by C. W. Kearns et al. (J. Econ. Entomol., 1949, 42, 27). Introduced by J. Hyman & Co. and by Shell International Chemical Co., Ltd. Patents US 2635977 (to Hyman) APPLICATIONS: Biochemistry Antagonist of the GABA receptor-chloride channel complex. Mode of action Non-systemic insecticide with contact, stomach, and respiratory action. Uses Control of soil-dwelling insects including termites and ants at 0.5–5.0 kg/ha. Also used for wood preservation. Formulation types DP; EC; WP; GR. PRODUCTS: Discontinued products ‘Aldrex’* (Shell); ‘Octalene’* (Sandoz). ANALYSIS: TC and formulation analysis by i.r. spectrometry (CIPAC Handbook, 1983, 1B, 1706; AOAC Methods, 18th Ed., 961.05), by tlc (ibid., 972.05), by potentiometric titration of liberated chloride ion (CIPAC Handbook, 1994, F, 190), or by glc. Residues determined by glc, tlc or paper chromatography (AOAC Methods, 18th Ed., 970.52), or by glc with ECD (Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 268; Analyst (London), 1979, 104, 425; P.A.Greve & W. B. F. Grevenstuk, Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1975, 40, 1115; G. M. Telling, J. Chromatogr., 1977, 137, 405; M. A. Luke et al., J. Assoc. Off. Anal. Chem., 1981, 64, 1187). See also Pestic. Anal. Man., I, 208, 303, 503. In drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 91 (1989). JMPR Mtg. 65 (1992); JMPR Evaln. I 66 (1992); JMPR Evaln. 29 (1977). HSG 21 (1989). PDS 41 (1979). ICSC.774 (1998). IARC 5 (1974); Suppl. 7 (1987). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EC, as amended by Regulation 850/2004. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for rats 38–67, guinea pigs 33, rabbits 50–80, dogs 65–95 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 15–25, rats 98 mg/kg. Toxic by skin absorption. NOEL LOAEL 0.025 mg/kg b.w. (EPA IRIS) ADI/RfD (JMPR) 0.0001 mg/kg b.w. (PTDI) [1994] (aldrin + dieldrin); (EPA) cRfD 0.00003 mg/kg b.w. [1988]. Water GV 0.03 μ;g/l (sum of aldrin+dieldrin). Other Because aldrin is rapidly epoxidised 10 The Pesticide Manual Sixteenth Edition © BCPC 2012 allidochlor in living tissue, forming dieldrin (q.v.), the long term toxicology of dieldrin to laboratory animals can be regarded as representative of aldrin. Toxicity Class WHO (a.i.) Ib EPA (formulation) I EC Classifcation T; R24/25, R48/24/25| R40| N; R50, R53 PIC Yes. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 6.59, mallard 52 mg/kg. Fish LC 50 (24 h) 0.018– 0.089 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Animals In living organisms, aldrin is rapidly epoxidised to dieldrin (q.v.). Soil/Environment In soil and water, undergoes epoxidation to dieldrin (q.v.). Details PM8, Entry 00120. allidochlor Herbicide NOMENCLATURE: Common name allidochlor (BSI, E-ISO); alidochlore ((m) F-ISO); CDAA (WSSA, JMAF) IUPAC name N,N-diallyl-2-chloroacetamide Chemical Abstracts name 2-chloro-N,N-di-2-propenylacetamide CAS RN [93–71–0] EC no 202–270–7 Development codes CP 6343 (Monsanto) Smiles code ClCC(=O)N(CC=C)CC=C PHYSICAL CHEMISTRY: Mol. wt. 173.6 M.f. C 8 H 12 ClNO Form Amber-coloured oil. B.p. 74 °C /0.3 mmHg V.p. 1250 mPa (20 °C) K ow logP = 0.97 (Agchem. Desk Ref.) S.g./ density 1.088 (25 °C) Solubility In water 20 g/kg (25 °C). In chlorobenzene, chloroform, cyclohexanone, ethanol, and xylene >500 g/kg (25 °C); in hexane >200 g/kg (36 °C). Stability Stable to uv light; decomposes at 125 °C. COMMERCIALISATION: History Herbicide reported by P. C. Hamm & A. J. Speziale (J. Agric. Food Chem., 1956, 4, 518). Introduced by Monsanto Co. Patents US 2864683 APPLICATIONS: Biochemistry Inhibition of cell respiration. Mode of action Selective herbicide Uses A selective pre-em. herbicide used to control annual grasses and certain broad-leaved weeds in beans (various types), cabbages, celery, certain fruits, maize, onions, certain ornamentals, sugar cane and sweet potatoes. Incorporated into soil after pre-em. application; also used post-em. and absorbed by cotyledons of grass seedlings. Formulation types EC; GR. PRODUCTS: Discontinued products ‘Randox’* (Monsanto); Discontinued mixtures ‘Randox-T’* (+ trichlorobenzyl chloride) (Monsanto). ANALYSIS: Product and residue analysis is by glc. Supplementary Entries – Extended allyl alcohol 11 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 700 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 830 mg tech./kg. Corrosive to skin and eyes (rabbits). NOEL In 90 d feeding trials, no adverse effect observed in rats and dogs at 200 mg/kg diet (highest rate tested). Toxicity Class WHO (a.i.) II EC Classifcation Xn; R21/22| Xi; R36/38| N; R51, R53 ECOTOXICOLOGY: Fish LC 50 for rainbow trout 2.0 mg/l. Bees Not toxic to bees when used as prescribed. ENVIRONMENTAL FATE: Plants In plants, it is readily metabolised to glycollic acid and diallylamine. Soil/Environment Rapid hydrolytic cleavage of chlorine atom with formation of water- soluble metabolites. There is oxidative attack on the allyl group. Glycolic acid is also a metabolite. Loss from soil is mainly by microbial activity, but soil incorporation is needed because of its volatility. Duration of activity 3–6 weeks, depending on soil. Details PM7, Entry 00140. allyl alcohol Herbicide NOMENCLATURE: Common name allyl alcohol (BSI, ISO, accepted in lieu of common name) IUPAC name allyl alcohol; prop-2-en-1-ol Chemical Abstracts name 2-propen-1-ol CAS RN [107–18–6] EC no 203–470–7 PHYSICAL CHEMISTRY: Mol. wt. 58.08 M.f. C 3 H 6 O Form Colourless, mobile liquid with a pungent odour. M.p. forms a glass at –190 °C B.p. 96.9 °C V.p. 2.31 × 10 6 mPa (20 °C) S.g./density 0.8535 at 20 °C Solubility Miscible with water and common organic solvents. Stability Polymerises on storage and therefore requires the addition of a stabiliser. Stable in uv light. F.p. 32 °C (open cup) COMMERCIALISATION: History Its experimental use as a herbicide frst reported in 1950. APPLICATIONS: Mode of action Inhibits germination. Uses Herbicide for control of weed and grass seeds. Applied to nursery, forestry, vegetable, tobacco, and other seeds beds, at 85–170 g in 50 000–100 000 l water/ha. Also for the partial sterilisation of glasshouse soil (E. M. Emmert & J. E. Klinker, Ky. Agric. Exp. Stn. Prog. Rep., 1950) at 18.4 g in 6.1 l water/m 2 of soil. Formulation types TC. ANALYSIS: CH 2 CH H 2 C OH 12 The Pesticide Manual Sixteenth Edition © BCPC 2012 allyxycarb Product analysis by measurement of the bromine added across the double-bond or acetylation of the hydroxyl group in the presence of pyridine. For a polarographic determination see M. Jaworski and J. Bogaczek (Chem. Anal. (Warsaw) 1969, 14, 1247–1251), reported in Fresenius’ Z. Anal. Chem. 1971, 257, 70. It may be detected by trapping in water or sulfuric acid and oxidising to acrylaldehyde by chromic-sulfuric acid. For detection of residues in soil before sowing, the biological cress root test is mostly applied. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC 0095 (2000). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 64, mice 85 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 89 mg/kg; absorbed rapidly through the skin. Lachrymatory and intensely irritating to skin and mucous membranes. Inhalation High inhalation toxicity. NOEL Highest oral dose without activity for male and female rats 4.8 and 6.2 mg/kg daily (15 w). ADI/RfD (EPA) cRfD 0.005 mg/kg b.w. [1989]. Other Maximum acceptable concentration in work-place atmosphere over an 8-hour work period 5 mg/m 3 . Toxicity Class WHO (a.i.) Ib EC Classifcation R10| T; R23/24/25| Xi; R36/37/38| N; R50 ECOTOXICOLOGY: Fish Toxic to fsh. Bees Not toxic to bees when used as prescribed. ENVIRONMENTAL FATE: Soil/Environment Metabolism not known. It disappears for the most part through evaporation. Duration of activity 3–10 days depending on temperature, soil type, and humidity. Details PM6, p. 9. allyxycarb Insecticide NOMENCLATURE: Common name allyxycarb (BSI, E-ISO); allyxycarbe (F-ISO); APC (JMAF) IUPAC name 4-diallylamino-3,5-xylyl methylcarbamate Chemical Abstracts name 4-(di-2-propenylamino)-3,5-dimethylphenyl methylcarbamate CAS RN [6392–46–7] Development codes Bayer 50 282; A 546 Smiles code CNC(=O)Oc1cc(C)c(N(CC=C)CC=C)c(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 274.4 M.f. C 16 H 22 N 2 O 2 COMMERCIALISATION: History Insecticide introduced by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Supplementary Entries – Extended amibuzin 13 TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Details PM4, p. 10. alorac Plant growth regulator NOMENCLATURE: Common name alorac (BSI, E-ISO, (m) F-ISO) IUPAC name (Z)-perchloro-4-oxopent-2-enoic acid; (Z)-2,3,5,5,5-pentachloro-4-oxopent-2-enoic acid Chemical Abstracts name (Z)-2,3,5,5,5-pentachloro-4-oxo-2-pentenoic acid CAS RN [19360–02–2] Smiles code OC(=O)/C(=C(/Cl)\C(=O)C(Cl)(Cl)Cl)/Cl; without stereochemistry:OC(=O)C(=C(Cl)C(=O)C(Cl)(Cl)Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 286.3 M.f. C 5 HCl 5 O 3 COMMERCIALISATION: History Plant growth regulator. ametridione Herbicide NOMENCLATURE: Common name amé(tridione) ((m) F-ISO); ametridione (BSI, E-ISO) IUPAC name 1-amino-6-ethylthio-3-neopentyl-1,3,5-triazine-2,4(1H,3H)-dione Chemical Abstracts name 1-amino-3-(2,2-dimethylpropyl)-6-(ethylthio)-1,3,5-triazine- 2,4(1H,3H)-dione CAS RN [78168–93–1] Development codes BAY SSH 0860 Smiles code CCSc1nc(=O)n(CC(C)(C)C)c(=O)n1N PHYSICAL CHEMISTRY: Mol. wt. 258.3 M.f. C 10 H 18 N 4 O 2 S COMMERCIALISATION: History Herbicide evaluated by Bayer AG. amibuzin Herbicide NOMENCLATURE: Common name amibuzine ((f) F-ISO); amibuzin (BSI, E-ISO) IUPAC name 6-tert-butyl-3-dimethylamino-4-methyl-1,2,4-triazin-5(4H)-one 14 The Pesticide Manual Sixteenth Edition © BCPC 2012 amidochlor Chemical Abstracts name 3-(dimethylamino)-6-(1,1-dimethylethyl)-4-methyl-1,2,4- triazin-5(4H)-one CAS RN [76636–10–7] Development codes DIC 3202 Smiles code CN(C)c1nnc(c(=O)n1C)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 210.3 M.f. C 10 H 18 N 4 O COMMERCIALISATION: History Herbicide developed by Bayer AG. amidithion Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name amidiphos ((m) France); amidithion (BSI, E-ISO, (m) F-ISO, ESA, ex-ANSI) IUPAC name S-2-methoxyethylcarbamoylmethyl O,O-dimethyl phosphorodithioate; 2-dimethoxyphosphinothioylthio-N-(2-methoxyethyl)acetamide Chemical Abstracts name S-[2-[(2-methoxyethyl)amino]-2-oxoethyl] O,O-dimethyl phosphorodithioate CAS RN [919–76–6] Development codes Ciba 2446 Smiles code COCCNC(=O)CSP(=S)(OC)OC PHYSICAL CHEMISTRY: Mol. wt. 273.3 M.f. C 7 H 16 NO 4 PS 2 COMMERCIALISATION: History Acaricide and insecticide (V. Dittrich & F. Bachman, Proc. Br. Insectic. Fungic. Conf., 2nd, 1963, p. 421). Introduced by Ciba AG (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22 Details PM2, p. 16. amidochlor Plant growth regulator NOMENCLATURE: Common name amidochlor (ANSI) IUPAC name N-acetamidomethyl-2-chloro-2′,6′-diethylacetanilide Chemical Abstracts name N-[(acetylamino)methyl]-2-chloro-N-(2,6-diethylphenyl) acetamide CAS RN [40164–67–8] Development codes MON 4620; CP-76 963 Supplementary Entries – Extended aminocarb 15 Smiles code CCc1cccc(CC)c1N(CNC(=O)C)C(=O)CCl PHYSICAL CHEMISTRY: Mol. wt. 296.8 M.f. C 15 H 21 ClN 2 O 2 COMMERCIALISATION: History Plant growth regulator introduced by Monsanto Co. PRODUCTS: Discontinued products ‘Limit’* (Monsanto). amidothioate Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name amidothioate (JMAF) IUPAC name O-2-chloro-4-methylthiophenyl O-methyl ethylphosphoramidothioate Chemical Abstracts name O-[2-chloro-4-(methylthio)phenyl] O-methyl ethylphosphoramidothioate CAS RN [54381–26–9] Development codes NK-11 Smiles code CCNP(=S)(OC)Oc1ccc(SC)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 311.8 M.f. C 10 H 15 ClNO 2 PS 2 COMMERCIALISATION: History Acaricide introduced by Nippon Kayaku Co., Ltd. APPLICATIONS: Biochemistry Cholinesterase inhibitor. aminocarb Insecticide IRAC 1A NOMENCLATURE: Common name aminocarb (BSI, E-ISO, ESA); aminocarbe ((m) F-ISO) IUPAC name 4-dimethylamino-m-tolyl methylcarbamate Chemical Abstracts name 4-(dimethylamino)-3-methylphenyl methylcarbamate Other names DTMC CAS RN [2032–59–9] EC no 217–990–7 Development codes Bayer 44 646; A 363 Smiles code CNC(=O)Oc1ccc(N(C)C)c(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 208.3 M.f. C 11 H 16 N 2 O 2 Form Colourless crystalline solid. M.p. 93–94 °C V.p. 2.3 mPa (EPA, 1988) Solubility In water 915 mg/ kg (20 °C) (Agchem. Desk Ref.). Moderately soluble in aromatic solvents; soluble in polar organic solvents. COMMERCIALISATION: 16 The Pesticide Manual Sixteenth Edition © BCPC 2012 amiprofos-methyl History Insecticide reported by G. Unterstenhöfer (Meded. Landbouwhogesch. Opzoekingsstn. Staat Gent, 1963, 28, 758). Introduced by Bayer AG. Patents DE 1145162 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide with contact and stomach action. Uses Mainly used against lepidopterous larvae and other chewing insects; generally recommended at 75 g/100 l. Formulation types WP. Compatibility Incompatible with highly alkaline pesticides. PRODUCTS: Discontinued products ‘Matacil’* (Bayer); ‘Metacil’* (Bayer). ANALYSIS: Product analysis by rplc (CIPAC Handbook, 1988, D, 7) or lc (AOAC Methods, 18th Ed., 985.02; J. Assoc. Off. Anal. Chem., 1985, 68, 372, 6.A25–6.A30) or by uv spectroscopy (H. Niessen & H. Frehse, Pfanz.-Nachr. Bayer (Engl. Ed.), 1963, 16, 205). Residues determined by uv spectroscopy or by glc of a derivative (R. J. Argauer, J. Agric. Food Chem., 1969, 17, 888; E. R. Holden et al., ibid., p.56; L. I. Butler & L. M. McDonough, ibid., 1968, 16, 403). See also Pestic. Anal. Man., I, 302. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). JMPR Evaln. 33 (1979). ICSC 0097 (1994). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 30–50 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 275 mg/kg. NOEL In 2 y feeding trials, rats receiving 200 mg/kg diet showed no symptom of poisoning. ADI/RfD (JMPR) No ADI [1979]. Other Acute i.p. LD 50 for rats 21 mg/kg. Toxicity Class WHO (a.i.) Ib EC Classifcation T; R24/25| N; R50, R53 ECOTOXICOLOGY: Bees Toxic to bees. Details PM8, Entry 00270. amiprofos-methyl Herbicide HRAC K1 WSSA 3; phosphoroamidate NOMENCLATURE: Common name amiprofos-methyl (BSI, E-ISO, (m) F-ISO) IUPAC name O-methyl O-2-nitro-p-tolyl isopropylphosphoramidothioate Chemical Abstracts name O-methyl O-(4-methyl-2-nitrophenyl) (1-methylethyl) phosphoramidothioate Other names amiprophos-methyl CAS RN [36001–88–4] Development codes BAY NTN 6867; NTN 2925 Smiles code COP(=S)(NC(C)C)Oc1ccc(C)cc1[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 304.3 M.f. C 11 H 17 N 2 O 4 PS Supplementary Entries – Extended ampropylfos 17 COMMERCIALISATION: History Herbicide reported by M. Aya et al. (Zasso Kenkyu, 1973, (15), p. 20). Evaluated by Bayer AG. APPLICATIONS: Biochemistry Microtubule assembly inhibition. amiton; amiton hydrogen oxalate Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name amiton (BSI) IUPAC name S-2-diethylaminoethyl O,O-diethyl phosphorothioate Chemical Abstracts name S-[2-(diethylamino)ethyl] O,O-diethyl phosphorothioate CAS RN [78–53–5] amiton; [3734–97–2] amiton hydrogen oxalate Development codes R 5158 (amiton); R 6199 (amiton hydrogen oxalate) PHYSICAL CHEMISTRY: Mol. wt. 269.3; (oxalate 359.4) M.f. C 10 H 24 NO 3 PS; (oxalate C 12 H26NO7PS) COMMERCIALISATION: History Insecticide and acaricide reported by R. Ghosh & J. F. Newman (Chem. Ind. (London), 1955, p. 118) and by G. L. Baldit (J. Sci. Food Agric., 1958, 9, 516). Evaluated by Plant Protection Ltd (later ICI Agrochemicals). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Tetram’* (oxalate) (ICI). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). ampropylfos Fungicide NOMENCLATURE: Common name ampropylfos (BSI, E-ISO, (m) F-ISO) IUPAC name (RS)-1-aminopropylphosphonic acid HO P OH CHCH 2 CH 3 O NH 2 18 The Pesticide Manual Sixteenth Edition © BCPC 2012 ampropylfos Chemical Abstracts name (±)-(1-aminopropyl)phosphonic acid CAS RN [16606–64–7] Development codes PNL-62 Smiles code CCC(N)P(=O)(O)O PHYSICAL CHEMISTRY: Mol. wt. 139.1 M.f. C 3 H 10 NO 3 P Form White solid. M.p. 264–270 °C V.p. 3.7 × 10 –3 mPa (90 °C) K ow logP = 3 S.g./density 0.5 Solubility In water 139 g/l (21 °C). In methanol 0.46, isopropanol 0.003, hexane, toluene, dichloromethane, ethyl acetate, and acetone ≤0.0001 (all in g/l, 21 °C). Stability Stable ≥2 y (pH 4–7, 20 °C); stable >31 d (pH 9, 25 °C); stable ≥3 d (pH 4, 100 °C). pKa pKa2 5.9, pKa3 10.4 COMMERCIALISATION: History Fungicide discovered by KenoGard AB (later Rhône-Poulenc Agrochimie). Manufacturers Rhône-Poulenc APPLICATIONS: Uses Control of covered smut, loose smut, Fusarium spp., leaf stripe, and net blotch in barley, and leaf stripe and loose smut in oats. Formulation types SC. PRODUCTS: Discontinued mixtures ‘Ravyl’* (+ anthraquinone + myclobutanil) (Bayer). ANALYSIS: Product by hplc with uv detection at 220 nm. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Non-sensitising to skin (guinea pigs). Non-irritating to skin of rabbits. Inhalation LC 50 for rats >4 mg/l air. NOEL (90 d) for rats 100 mg/kg daily (only minimal changes at 300 mg/kg daily). In 90 d feeding trials, 0.1% PNL 62 in the diet had no effect on dogs after 13 w treatment (effects at 0.5% were minimal and there is no evidence of systemic or target organ toxicity). Non-teratogenic to rats at 1000 mg/kg daily. Non- teratogenic to rabbits at 10 mg/kg daily. Other Intravenous LD 50 for rats c. 1250 mg/kg. Non-mutagenic in the Ames test and other mutagenicity tests. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail and mallard ducks >2000 mg/kg. Dietary LC 50 for bobwhite quail and mallard ducks >5000 mg/kg. No observed neurotoxicity to hens. Fish LC 50 (96 h) for rainbow trout, bluegill sunfsh, and mirror carp >135 mg/l. Daphnia LC 50 (24 and 48 h) >100 mg/l. Algae EC 50 for Selenastrum capricornutum 54 mg/l. Worms LC 50 for Eisenia foetida >1000 mg/kg. ENVIRONMENTAL FATE: Animals After oral administration to rats of a single dose of 200 mg ampropylfos/kg b.w. there is a rapid absorption (about 50%) with peak concentration 1 h after dosage, and a fast decline in a bioexponential manner with DT 50 c. 2 h in plasma, 50 h in blood. Similar Supplementary Entries – Extended anabasine 19 decline is found after intravenous administration in rats. Whole body autoradiograms of rats showed that 14 C-labelled ampropylfos is widely distributed in tissues as well as being taken up to some extent into bone and blood cells. There is no evidence of 14 C-labelled ampropylfos-related material crossing either the placental or blood brain barriers. Plants Uptake of 14 C-labelled ampropylfos (applied as a seed dressing formulation at a level of 400 mg/kg seed) from seeds of winter barley is very low. Soil/Environment Ampropylfos is strongly bound to soil. The percentage of applied 14 C-labelled ampropylfos eluted from three standard soil types was 0.61 (sand), 0.035 (loamy sand), 0.925 (sandy loam) ( 14 C-labelled ampropylfos applied in an amount corresponding to a feld application rate of 1500 g/ha and water added equivalent to 200 mm rain). Ampropylfos is readily biodegradable in freshwater to levels of 81% and 79% within 35 days at 22.5 ±2.5 °C using unacclimatised and acclimatised inocula, respectively. No photodegradation of ampropylfos was observed in artifcial sunlight after 34 days of continuous irradiation in pH 5, pH 7, and pH 9 buffered aqueous solutions at 25 °C (1 day of artifcial sunlight was equivalent to 1.25 days of natural sunlight). Details PM9, Entry 0375. anabasine Insecticide NOMENCLATURE: Common name anabasine (JMAF) IUPAC name (S)-3-(piperidin-2-yl)pyridine Chemical Abstracts name (S)-3-(2-piperidinyl)pyridine Other names 2-(3-pyridyl) piperidine CAS RN [494–52–0]; [13078–04–1] racemate Smiles code C1CCC(NC1)c2cccnc2 PHYSICAL CHEMISTRY: Mol. wt. 162.2 M.f. C 10 H 14 N 2 M.p. Freezes 9 °C B.p. 281 °C S.g./density 1.048 (20 °C) Solubility Miscible with water and most organic solvents. COMMERCIALISATION: Production Obtained, as racemic material, from Nicotiana glauca. History Insecticide isolated in 1931 from Anabasis aphylla. APPLICATIONS: Biochemistry Agonist of nicotine acetylcholine receptors. 20 The Pesticide Manual Sixteenth Edition © BCPC 2012 anilazine anilazine Fungicide FRAC M8, M; multi-site: triazine fungicide NOMENCLATURE: Common name anilazine (BSI, E-ISO, (f) F-ISO); triazine (JMAF) IUPAC name 4,6-dichloro-N-(2-chlorophenyl)-1,3,5-triazin-2-amine; 2-chloro-N-(4,6- dichloro-1,3,5-triazin-2-yl)aniline Chemical Abstracts name 4,6-dichloro-N-(2-chlorophenyl)-1,3,5-triazin-2-amine CAS RN [101–05–3] EC no 202–910–5 Development codes B-622 (Ethyl Corp.) Smiles code Clc1ccccc1Nc2nc(Cl)nc(Cl)n2 PHYSICAL CHEMISTRY: Mol. wt. 275.5 M.f. C 9 H 5 Cl 3 N 4 Form Colourless to tan crystals. M.p. 159 °C V.p. 8.2 × 10 –4 mPa (20 °C) K ow logP = 3.02 (20 °C) Henry 2.82 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.8 (20 °C) Solubility In water 8 mg/l (20 °C). In acetone 100, chlorobenzene 60, toluene 50, xylene 40 (all in g/l, 30 °C). In dichloromethane 90, isopropanol 8, hexane 1.7 (all in g/l, 20 °C). Stability Stable in neutral and slightly acidic media. Hydrolysed on heating with alkalis; DT 50 (22 °C) 730 h (pH 4), 790 h (pH 7), 22 h (pH 9). COMMERCIALISATION: History Fungicide reported by C. N. Wolf et al. (Science, 1955, 121, 61). Introduced by the Ethyl Corp. and later by Nippon Soda Co., Ltd and by Bayer AG. Patents US 2720480 (to Ethyl Corp.) Manufacturers Bayer CropScience APPLICATIONS: Biochemistry Multi-site action. Mode of action Non-systemic foliar fungicide, with protective action. Uses Control of Septoria spp. of wheat (glume blotch and on leaves) was the main area of use. Also used for the control of early and late blights of potatoes and tomatoes; anthracnose in cucurbits; leaf spot diseases (Alternaria, Cercospora, and Septoria spp.) in many crops; Helminthosporium spp. in wheat and barley; brown patch, dollar spot, snow mould, and other diseases of turf; Botrytis, Colletotrichum, Leptosphaeria, and Pyrenophora spp. on many crops; etc. Also used on vegetables, ornamentals, berry fruit, melons, water melons, coffee, and tobacco. Formulation types WP; SC. Compatibility Incompatible with oils and alkaline materials. PRODUCTS: Discontinued products ‘Dyrene’* (Bayer); ‘Kemate’* (Bayer); ‘Triazine’* (Nippon Soda); ‘Triazin Jet’* (Nippon Soda). N N N NH Cl Cl Cl Supplementary Entries – Extended anisuron 21 ANALYSIS: Product analysis by lc (AOAC Methods, 18th Ed., 988.04; CIPAC Handbook, 1992, E, 5) or by hydrolysis and measurement of the chloride liberated (P. F. Kane & K. G. Gillespie, J. Agric. Food Chem., 1960, 8, 29). Methods for determination of residues were available from Bayer. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Mtg. 65 (1992); JMPR Evaln. I 66 (1992); JMPR Evaln. II 58 (1989). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >4000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Severe eye irritant; mild skin irritant (rabbits). Inhalation LC 50 for rats (4 h) >0.25 mg/l air (aerosol), (1 h) >0.7 mg/l air (dust). NOEL (2 y) for rats 2000, mice 1250 mg/kg diet; (18 mo) for dogs 40 mg/kg b.w. ADI/RfD (JMPR) 0.1 mg/kg b.w. [1989]; (EPA) 0.0004 mg/kg b.w. [1989]. Toxicity Class WHO (a.i.) U; (WHO Recommended Classifcation gives O) EPA (formulation) II EC Classifcation Xi; R36/38| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for Virginia quail >2000 mg/kg b.w. LC 50 (5 d) for mallard ducks >5000 mg/kg. Fish LC 50 (96 h) for rainbow trout and golden orfe 0.15 mg/l. Daphnia LC 50 (48 h) 0.07 mg/l. Bees Not harmful to bees at recommended application rates. ENVIRONMENTAL FATE: Animals Elimination is quick; almost 98% is excreted within 72 h in the urine and faeces. Plants In plants, one or both chlorine atoms in the triazine ring are substituted by amino or thio groups, through reaction with amino acids, peptides, coenzymes, and other endogenous substances in the cellular system of the plant (R. G. Owens Ann. New York Acad. Sci. 1969, 160, 114–132). Soil/Environment DT 50 in damp soilc. 12 h. Readily degraded in different soils. Details PM10, Entry 29. anisuron Herbicide NOMENCLATURE: Common name anisuron (BSI) IUPAC name 1-(3,4-dichlorophenyl)-1-(4- methoxybenzoyl)-3,3-dimethylurea Chemical Abstracts name N-(3,4-dichlorophenyl)- N-[(dimethylamino)carbonyl]-4-methoxybenzamide CAS RN [2689–43–2] Smiles code COc1ccc(cc1)C(=O)N(C(=O)N(C)C)c2ccc(Cl)c(Cl)c2 PHYSICAL CHEMISTRY: Mol. wt. 367.2 M.f. C 17 H 16 Cl 2 N 2 O 3 COMMERCIALISATION: History Herbicide. 22 The Pesticide Manual Sixteenth Edition © BCPC 2012 antu antu Rodenticide NOMENCLATURE: Common name antu (BSI, E-ISO, (m) F-ISO, JMAF) IUPAC name 1-(1-naphthyl)-2-thiourea Chemical Abstracts name 1-naphthalenylthiourea Other names α-naphthylthiourea CAS RN [86–88–4] EC no 201–706–3 Smiles code NC(=S)Nc1cccc2ccccc12 PHYSICAL CHEMISTRY: Mol. wt. 202.3 M.f. C 11 H 10 N 2 S Form Colourless crystals; (tech. is a blue-grey powder). M.p. 198 °C Solubility In water 600 mg/l (room temperature). In acetone 24.3, triethyleneglycol 86 (both g/l, room temperature). Stability Stable on exposure to air and to sunlight. COMMERCIALISATION: History Toxicity to rodents reported by C. F. Richter (J. Am. Med. Assoc., 1945, 129, 927; Proc. Soc. Exp. Biol. Med., 1946, 63, 364). Patents US 2390848 APPLICATIONS: Uses A rodenticide specifc for adult Rattus norvegicus for which the toxic dose is 6–8 mg/kg. It is less toxic to other Rattus spp. and tolerance is developed in rats by repeated administration of sub-lethal doses. Formulation types RB; CP. ANALYSIS: Product analysis is by reaction with silver nitrate and titration of the liberated nitric acid. (CIPAC Handbook, 1970, 1, 16; AOAC Methods, 18th Ed., 948.03, see 10th Ed., 4.132). Residues determined by colorimetry of a derivative (E. Bremais & K. G. Bergner, Pharm. Zentralhalle, 1950, 89, 115). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.973 (2000). IARC 30 (1983); suppl. 7 (1987). MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for Norwegian rats 6–8 mg/kg; less toxic for other rat species; surviving rats develop tolerance. Acute oral LD 50 for monkeys 4250, dogs 38 mg/kg. Relatively safe for domestic animals; induces vomiting in dogs. Pigs are very sensitive. Very low human toxicity. Other Naphthylamines, present as impurities, are carcinogenic. Toxicity Class WHO (a.i.) Ib EC Classifcation T+; R28| R40 ECOTOXICOLOGY: Birds Chickens are very sensitive. ENVIRONMENTAL FATE: Animals In rats, following oral administration, 40% is eliminated within 20 h. Metabolised by lung and liver microsomal preparations into 1-naphthylurea and sulfur. Details PM8, Entry 00450. Supplementary Entries – Extended arsenous oxide 23 aramite Acaricide NOMENCLATURE: Common name aramite (JMAF) IUPAC name 2-(4-tert-butylphenoxy)-1-methylethyl 2-chloroethyl sulfte Chemical Abstracts name 2-chloroethyl 2-[4-(1,1-dimethylethyl)phenoxy]-1- methylethyl sulfte CAS RN [140–57–8] Development codes 88-R Smiles code CC(COc1ccc(cc1)C(C)(C)C)OS(=O)OCCCl PHYSICAL CHEMISTRY: Mol. wt. 334.9 M.f. C 15 H 23 ClO 4 S COMMERCIALISATION: History Acaricide reported by W. D. Harris & J. W. Zukel (J. Agric. Food Chem., 1954, 2, 140). Introduced by Uniroyal Chemical Co., Inc. PRODUCTS: Discontinued products ‘Aramite’* (Uniroyal); ‘Niagaramite’* (FMC). ANALYSIS: Residues determined colorimetrically (AOAC Methods, 18th Ed., 959.10, see 12th Ed., 29.067–29.071). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: IARC 5 (1974). EU Status (1107/2009) Never notifed to the EU. MAMMALIAN TOXICOLOGY: IARC Class 2B Toxicity Class WHO (a.i.) O Details PM3, p. 73. arsenous oxide Rodenticide NOMENCLATURE: Common name arsenious acid (JMAF); arsenous oxide (E-ISO, accepted in lieu of a common name); oxyde arsenieux (F-ISO, accepted in lieu of a common name.) IUPAC name diarsenic trioxide; arsenic trioxide Chemical Abstracts name arsenic oxide (As2O3) Other names arsenious oxide; white arsenic CAS RN [1327–53–3] EC no 215–481–4 Smiles code o1[as]2o[as]3o[as]1o[as](o2)o3 PHYSICAL CHEMISTRY: Mol. wt. 395.7 M.f. As 4 O 6 Form Colourless solid which exists in rhombic, octahedral and amorphous forms. The amorphous form is unstable, reverting to the octahedral. M.p. 272 °C, subliming 125–150 °C (octahedral); 312 °C (rhombic) V.p. 8.8 kPa (312 °C) (rhombic form) Solubility In water 17 g/l (16 °C). Practically insoluble in chloroform, diethyl ether, ethanol. Stability Stable in air but oxidised slowly in acid media. Dissolves in alkali to form arsenites. 24 The Pesticide Manual Sixteenth Edition © BCPC 2012 asomate COMMERCIALISATION: History Used as a rodenticide since the 16th century. APPLICATIONS: Uses Used in baits to control Rattus norvegicus, R. rattus and Mus musculus. It has also been used as a sheep dip to control ectoparasites. Formulation types PA . ANALYSIS: Product analysis by titration with iodine (WHO Specifcations Insectic. (2nd Ed.). Residues determined by atomic absorption spectroscopy (AOAC Methods, 14th Ed., 25.001–25.007) by colorimetry (ibid., 25.041–25.055) or by the Gutzeit method (ibid., 25.045; 12th Ed., 25.006–25.009). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 224 (2001). HSG 70 (1992). ICSC.378 (1997). IARC 23 (1980), Suppl 7 (1987). MAMMALIAN TOXICOLOGY: IARC Class 1 (evaluation applies to arsenic compounds as a whole, not necessarily to all individual compounds within the group) Oral Acute oral LD 50 for rats 180–200 mg a.i. (in carbohydrate or protein)/kg, 300 mg (in bacon fat)/kg, 20 mg (in aqueous solution)/kg (E. Packman et al., J. Agric. Food Chem., 1961, 9, 271); for mice 34.4–63.5 mg/kg (J. W. E. Harrison, AMA Arch. Ind. Health, 1958, 17, 118). Other It is extremely toxic to man, the minimum lethal dose is 2 mg/kg (H. O. Calvery, J. Am. Med. Assoc., 1938, 111, 1722). It is non-cumulative and is eliminated from the animal body in 7–42 d. Evidence of carcinogenicity in humans. Toxicity Class WHO (a.i.) Ia (sodium arsenite Class Ib) EC Classifcation R45| T+; R28| C; R34| N; R50, R53 Details PM9, Entry 460. asomate Chemosterilant NOMENCLATURE: IUPAC name arsinetriyl tris(dimethyldithiocarbamate); 1-{[bis(dimethylthiocarbamoyls ulfanyl)arsanyl]sulfanyl}-N,N-dimethylmethanethioamide; tris(dimethylthiocarbamoylthio) arsine Chemical Abstracts name N,N-dimethylcarbamodithioic acid anhydrosulfde with arsenotrithious acid (3:1); tris(dimethyldithiocarbamato)arsenic As S S S N S CH 3 H 3 C N Me Me S N S H 3 C CH 3 Supplementary Entries – Extended atraton 25 Other names TDDA; TTCA CAS RN [3586–60–5] Smiles code S=C(N(C)C)S[As](SC(N(C)C)=S)SC(N(C)C)=S PHYSICAL CHEMISTRY: Mol. wt. 435.6 M.f. C 9 H 18 AsN 3 S 6 Form Yellow-green crystals. APPLICATIONS: Mode of action Preventative and curative fungicide. Uses Used on apples and pears, powdery mildew of cucumber, grapes etc. Also for rice blast. Formulation types WP. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 335-370 mg/kg. Skin and eye Strong skin irritant. athidathion Insecticide IRAC 1B NOMENCLATURE: Common name athidathion (BSI, E-ISO, (m) F-ISO) IUPAC name O,O-diethyl S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl phosphorodithioate; 2-diethoxyphosphinothioylthiomethyl-5-methoxy-1,3,4-thiadiazol- 2(3H)-one Chemical Abstracts name O,O-diethyl S-[(5-methoxy-2-oxo-1,3,4-thiadiazol-3(2H)-yl) methyl] phosphorodithioate CAS RN [19691–80–6] Development codes G 13 006 Smiles code CCOP(=S)(OCC)SCn1nc(OC)sc1=O PHYSICAL CHEMISTRY: Mol. wt. 330.4 M.f. C 8 H 15 N 2 O 4 PS 3 COMMERCIALISATION: History Insecticide reported by K. Rüfenacht (Helv. Chim. Acta, 1968, 51, 518). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Deltacron’* (Geigy). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O atraton Herbicide NOMENCLATURE: Common name atraton (BSI, E-ISO, (f) F-ISO); atratone ((f) France, former name (BSI)) IUPAC name N 2 -ethyl-N4-isopropyl-6-methoxy-1,3,5-triazine-2,4-diamine 26 The Pesticide Manual Sixteenth Edition © BCPC 2012 azafenidin Chemical Abstracts name N-ethyl-6-methoxy-N′-(1-methylethyl)-1,3,5-triazine-2,4- diamine CAS RN [1610–17–9] Development codes G 32 293 Smiles code CCNc1nc(NC(C)C)nc(OC)n1 PHYSICAL CHEMISTRY: Mol. wt. 211.3 M.f. C 9 H 17 N 5 O M.p. 94–96 °C V.p. 3.8 mPa (20 °C) Henry 4.46 × 10 –4 Pa m 3 mol –1 (calc.) Solubility In water 0.18% (20 °C). Soluble in ketones, esters, ether, alcohols and other organic solvents. Stability Stable in neutral, weakly acidic and weakly basic media. Hydrolysed by warm acids and alkalis. COMMERCIALISATION: History Herbicide reported by E. Knüsli (Phytiatr.-Phytopharm., 1958, 7, 81). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Interferes with photosynthesis and other enzymic processes. Uses Selective herbicide used to protect sugar cane. Was also a component in total herbicide mixtures. Formulation types WP; EC. ANALYSIS: Product by extraction with ether and titration of one amino group with perchloric acid (Anal. Methods Pestic. Plant Growth Regul., 4, 28, 173). Residues by extraction with methylene chloride, hydrolysis with 0.1 N sulphuric acid, and spectrophotometric determination of the hydroxy derivative at 240 nm (Anal. Methods Pestic. Plant Growth Regul. 4, 28). For determination by tlc, spectrophotometry, and gc, see Man. Pestic. Residue Anal., 6A–C. For gc determination with prometon as internal standard, see Anal. Methods Pestic. Plant Growth Regul. 1972, 6, 597–599. In drinking water by glc with NPD (AOAC Methods, 18th Ed., 991.07). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1465–2400, mice 905 mg/kg. Skin and eye Feeding 50% atraton to rats at 10 and 200 mg/kg b.w. for 90 d produces no signs of illness. Toxicity Class WHO (a.i.) O ENVIRONMENTAL FATE: Soil/Environment Replacement of the methoxy group at C-2 by hydrolysis via the hydroxyl group. Dealkylation of the amino substituents at C-4 and C-6. Possibly opening of the triazine ring. azafenidin Herbicide N N N O Cl Cl O CH 2 C CH Supplementary Entries – Extended azafenidin 27 HRAC E WSSA 14; triazolinone NOMENCLATURE: Common name azafé(nidine) ((f) F-ISO); azafenidin (BSI, E-ISO) IUPAC name 2-(2,4-dichloro-5-prop-2-ynyloxyphenyl)-5,6,7,8-tetrahydro-1,2,4- triazolo[4,3-a]pyridin-3(2H)-one Chemical Abstracts name 2-[2,4-dichloro-5-(2-propynyloxy)phenyl]-5,6,7,8- tetrahydro-1,2,4-triazolo[4,3-a]pyridin-3(2H)-one CAS RN [68049–83–2] Development codes R6447; DPX-R6447; IN-R6447 (all DuPont) Smiles code Clc1cc(Cl)c(cc1OCC#C)n2nc3CCCCn3c2=O PHYSICAL CHEMISTRY: Composition Tech. isc. 97% pure. Mol. wt. 338.2 M.f. C 15 H 13 Cl 2 N 3 O 2 Form White powdered solid; (tech. is a rust-coloured solid with a pungent odour). M.p. 168–168.5 °C V.p. 1 × 10 –6 mPa (20 °C) K ow logP = 2.7 S.g./density 1.4 (20 °C) Solubility In water 16 ppm (pH 7). Stability Stable to hydrolysis; aqueous photolysis DT 50 c. 12 h. COMMERCIALISATION: History Evaluated by E. I. du Pont de Nemours & Co. Reported by L. Amuti et al. (Proc. Br. Crop Prot. Conf. – Weeds 1997, 1, p. 59). Manufacturers DuPont APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. Mode of action Absorbed through the roots and shoots. Weakly xylem or phloem mobile, hence has limited post-emergence activity. However, it improves the effcacy of other post-emergence herbicides, such as glyphosate, and increases the speed of action of contact herbicides. Uses Intended for use as a pre-emergence, and, in mixture, post-emergence, herbicide in citrus, grapes, olives, sugar cane and other perennial crops; active on both annual and perennial weeds, and applied at 240 g/ha. Formulation types WG . PRODUCTS: Discontinued products ‘Evolus’* (Europe) (DuPont); ‘Milestone’* (USA) (DuPont). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, 2002/949/EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Not an eye or skin irritant. Not a skin sensitiser. Inhalation LC 50 for rats >5.3 mg/l. NOEL (90 d) for male and female rats 50, male mice 50, female mice 300, dogs 10 ppm. Other Negative in Ames test. EC Classifcation T; R48/22| R61, R62| N; R50, R53| concn. dep. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail and mallard ducks >2250 mg/kg. LC 50 (8 d) for bobwhite quail and mallard ducks >5620 ppm. Fish LC 50 (96 h) for rainbow trout 33, bluegill sunfsh 48 mg/l. Daphnia EC 50 (48 h) 38 mg/l. Algae EC 50 (120 h) for Selenastrum capricornutum 0.94 μ;g/l. Bees LD 50 (oral) >20 μg/bee; (contact) >100 μg/bee. 28 The Pesticide Manual Sixteenth Edition © BCPC 2012 aziprotryne ENVIRONMENTAL FATE: Soil/Environment Degrades in soil by microbial and photolytic processes. In the feld, in a range of 4 soils, mean DT 50 c. 25 d, mean DT90c. 169 d. Mean K oc 298; there was minimal movement in soil column leaching studies and azafenidin is not expected to leach into groundwater. It is expected to dissipate rapidly through photolysis in natural waters. Details PM12, Entry 43. aziprotryne Herbicide NOMENCLATURE: Common name aziprotryne (BSI, E-ISO, (f) F-ISO); aziprotryn (USA) IUPAC name 4-azido-N-isopropyl-6-methylthio-1,3,5-triazin-2-ylamine Chemical Abstracts name 4-azido-N-(1-methylethyl)-6-(methylthio)-1,3,5-triazin-2- amine CAS RN [4658–28–0] Development codes C 7019 Smiles code CSc1nc(NC(C)C)nc(N=[N]=[N])n1 PHYSICAL CHEMISTRY: Mol. wt. 225.3 M.f. C 7 H 11 N 7 S Form Colourless crystalline powder. M.p. 94.5–95.5 °C V.p. 0.267 mPa (20 °C) Henry 1.09 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.40 (20 °C) Solubility In water 55 mg/l (20 °C). In acetone 27, dichloromethane 37, ethyl acetate 12, isopropanol 14, benzene 4 (all in g/kg, 20 °C). Stability Stable in neutral and slightly acidic media. Hydrolysed slowly in slightly alkaline media. COMMERCIALISATION: History Herbicide reported by D. H. Green et al. (C. R. Journ. Etud. Herbic. Conf. COLUMA, 4th, 1967, 1, 1). Introduced by Ciba AG (later Novartis Crop Protection AG). Patents BE 656233; GB 1093376 Manufacturers Novartis APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective herbicide, absorbed through the roots and foliage. Uses Control of a wide range of annual broad-leaved weeds and some grasses in brassicas (except caulifowers), onions, leeks, garlic, shallots, fennel, peas, beans, black salsify, and oilseed rape. Applied pre- or post-emergence. Phytotoxicity Phytotoxic to caulifowers. Formulation types WP. PRODUCTS: Discontinued products ‘Brasoran’* (Novartis); ‘Mesoranil’* (Ciba-Geigy). N N N CH 3 S NHCH(CH 3 ) 2 N 3 Supplementary Entries – Extended azobenzene 29 ANALYSIS: Product analysis by glc. Residues determined by glc using MCD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3600–5833 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3000 mg/kg. Mild eye irritant; non-irritating to skin. Inhalation LC 50 (6 h) for rats >0.208 mg/l. NOEL (90 d) for rats 50 mg/kg daily; for dogs 50 mg/kg daily. Toxicity Class WHO (a.i.) U EPA (formulation) III ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks and quail >4000 mg/kg. Fish LC 50 (96 h) for bluegill sunfsh and largemouth bass >1 mg/l. Bees Not toxic to bees. Details PM9, Entry 0550. azithiram Fungicide NOMENCLATURE: Common name azithiram (BSI, E-ISO); azithirame ((m) F-ISO) IUPAC name bis(3,3-dimethylthiocarbazoyl) disulfde; N,N′-bis(dimethylamino)thiuram disulfde Chemical Abstracts name 2,2,2′,2′-tetramethylthioperoxydicarbonic dihydrazide ([[(CH3)2NNH]C(S)]2S2) CAS RN [5834–94–6] Development codes PP447 Smiles code CN(C)NC(=S)SSC(=S)NN(C)C PHYSICAL CHEMISTRY: Mol. wt. 270.5 M.f. C 6 H 14 N 4 S 4 COMMERCIALISATION: History Fungicide evaluated by ICI Plant Protection Division (later ICI Agrochemicals). azobenzene Acaricide NOMENCLATURE: Common name azobenzene (BSI, E-ISO, F-ISO, accepted in lieu of a common name) IUPAC name azobenzene Chemical Abstracts name diphenyldiazene CAS RN [103–33–3] Smiles code N(=Nc1ccccc1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 182.2 M.f. C 12 H 10 N 2 COMMERCIALISATION: History Acaricidal activity reported by W. E. Blauvelt (N. Y. State Flower Grow. Bull., 1945, 30 The Pesticide Manual Sixteenth Edition © BCPC 2012 azoxybenzene No. 2). Was mainly used in glasshouses as a smoke. MAMMALIAN TOXICOLOGY: EC Classifcation R45; R40| Xn; R20/22 R48/22| N; R50/53 Details PM4, p. 27. azothoate Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name azothoate (BSI, E-ISO, (m) F-ISO) IUPAC name O-4-(4-chlorophenylazo)phenyl O,O-dimethyl phosphorothioate Chemical Abstracts name O-[4-[(4-chlorophenyl)azo]phenyl] O,O-dimethyl phosphorothioate CAS RN [5834–96–8] EC no 227–419–3 Development codes L 1058 Smiles code COP(=S)(OC)Oc1ccc(N=Nc2ccc(Cl)cc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 356.8 M.f. C 14 H 14 ClN 2 O 3 PS COMMERCIALISATION: History Insecticide and acaricide introduced by Montecatini S.p.A. (later Agrimont S.p.A.). APPLICATIONS: Biochemistry Cholinesterase inhibitor. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R20/22 azoxybenzene Acaricide, insecticide NOMENCLATURE: IUPAC name azoxybenzene Chemical Abstracts name diphenyldiazene 1-oxide Other names fenazox CAS RN [495–48–7] EC no 207–802–1 PHYSICAL CHEMISTRY: Mol. wt. 198.2 M.f. C 12 H 10 N 2 O Form Pale yellow needles. M.p. 38–38.5 °C V.p. 13 mPa (20 °C) S.g./density 1.159 (20 °C) Solubility In water 3.4 mg/kg (25 °C). In ethanol 285, groundnut oil 760 g/kg (26 °C); in ligroin 435 g/kg (10 °C). Stability Converted to o-hydroxyazobenzene by irradiation, and to p-hydroxyazobenzene in acidic media. Stable in strongly alkaline media. COMMERCIALISATION: Manufacturers Fahlberg-List Supplementary Entries – Extended barban 31 APPLICATIONS: Mode of action Non-systemic, with contact action. Uses Control of mites and whitefy on fruit trees, vines, hops, soya beans, ornamentals, vegetables and glasshouse crops. Formulation types EC. PRODUCTS: Discontinued products ‘Fentoxan’* (Fahlberg-List). ANALYSIS: Product by glc with FID. Residues by tlc, or by glc with ECD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 885 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 1350 mg/kg. NOEL (90 d) for rats 1 mg/kg daily. Other Non-carcinogenic and non-mutagenic. EC Classifcation Xn; R20/22 ECOTOXICOLOGY: Fish LC 50 (96 h) for carp 3, rainbow trout 2.7 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Plants Rapidly metabolised, initially to o-hydroxyazobenzene. barban Herbicide NOMENCLATURE: Common name chlorinat* (former exception, USSR); CBN (JMAF); barbanate (Republic of South Africa); barbane ((m) F-ISO); barban (BSI, E-ISO, ANSI, WSSA) IUPAC name 4-chlorobut-2-ynyl 3-chlorocarbanilate Chemical Abstracts name 4-chloro-2-butynyl (3-chlorophenyl)carbamate CAS RN [101–27–9] EC no 202–930–4 Development codes CS-847 (Spencer Chemicals) Smiles code ClCC#CCOC(=O)Nc1cccc(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 258.1 M.f. C 11 H 9 Cl 2 NO 2 Form Cystalline solid; (tech. is a tan solid). M.p. 75–76 °C; (tech., 60 °C) V.p. 0.05 mPa (25 °C) Henry 1.17 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.403 (25 °C, tech.) Solubility In water 11 mg/l (25 °C). In benzene 327, 1,2-dichloroethane 546, hexane 1.4, kerosene 3.9, xylene 279 (all in g/l, 25 °C). Stability Tech. decomposes at 224 °C. Stable under normal conditions of use; hydrolysis is very rapid in alkali with displacement of the terminal chlorine substituent, DT 50 58 sec (pH 13, 25 °C). COMMERCIALISATION: History Herbicide reported by A. D. Brown (Proc. North Cent. Weed Control Conf., 1958, 15, 98). Introduced by the Spencer Chemical Co. and later Velsicol Chemical Corp. Patents US 2906614 32 The Pesticide Manual Sixteenth Edition © BCPC 2012 barban APPLICATIONS: Biochemistry Acts by interfering with cell division. Mode of action Selective herbicide, absorbed principally by the foliage, with limited translocation in the apoplast. Uses A selective post-em. herbicide controlling wild oats in barley at the 1.5–2.5 leaf stage, and broad beans, feld fax, lentils, lucerne, mustard, oilseed rape, saffower, soya beans, sugar beet, sunfowers, wheat, Russian wild rye and other grasses. Phytotoxicity Phytotoxic to oats and some varieties of rye. Formulation types EC. PRODUCTS: Discontinued products ‘B25’* (FBC); ‘Carbyne’* (Spencer Chemicals). ANALYSIS: Product analysis by uv spectrometry (K. J. Bombaugh & W. C. Bull, J. Agric. Food Chem., 1961, 9, 386). Residues determined by hplc or by hydrolysis to 3-chloroaniline derivatives which are measured by glc (R. J. Harris & R. J. Whiteoak, Analyst (London), 1972, 97, 294). See also Pestic. Anal. Man., II, 180.268. In water, by lc with uv detection (AOAC Methods, 18th Ed., 992.14). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1376–1429 mg/kg. Skin and eye Acute percutaneous LD50 for rabbits >20 000, rats >1600 mg/kg. Mildly irritating to the skin of rabbits and produces a delayed skin sensitisation in guinea-pigs. It has been reported as a skin sensitiser in man; skin contact should be avoided by using plastic protective clothing. Inhalation LC 50 (4 h) for rats >28 mg/l air. NOEL (2 y) for rats 150 mg/kg diet, for dogs 5 mg/kg diet. In a 3-generation reproduction study in rats, NOEL 957 mg/kg diet Other Not teratogenic in rats at ≤87 mg/kg daily. Non-mutagenic to mammals by in vivo and in vitro tests. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| R43| N; R50, R53 ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks and bobwhite quail >10 000 mg/kg diet. Fish LC50 (96 h) for rainbow trout 0.6, bluegill sunfsh 1.2, goldfsh and guppies 1.3 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In rats and rabbits, barban is not easily absorbed through the skin. In rats, metabolism involves hydrolysis of the carbamate group, with formation of well known m-chloroaniline metabolites. There is no accumulation of barban or its metabolites in tissue, and they are rapidly excreted, principally in the urine. Plants Degraded rapidly in most plants. Metabolites include 3-chloroaniline and a glutathione conjugate. Soil/Environment In soil, degradation involves hydrolytic cleavage of the chlorobutynyl group, followed by decomposition of the carbamic acid so formed, with evolution of CO 2 , to give 3-chloroaniline. Duration of residual activity in soil, following an application rate of 3 l/ha, is c. 2–3 months. Details PM8, Entry 00620. Supplementary Entries – Extended barium polysulfde 33 barium carbonate Rodenticide NOMENCLATURE: Common name barium carbonate (JMAF) IUPAC name barium carbonate (I) Chemical Abstracts name (I) CAS RN [513–77–9] EC no 208–167–3 Smiles code [Ba+2].[O-]C(=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 197.3 M.f. CBaO 3 COMMERCIALISATION: History Used as a rodenticide for many years. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation barium salts (with exceptions) are Xn; R20/22 (concentration-dependent) Details PM5, p. 28. barium polysulfde Fungicide, insecticide NOMENCLATURE: Common name barium polysulfde (E-ISO, is accepted in lieu of a common name); polysulfure de baryum (F-ISO) IUPAC name barium polysulfde (I) Chemical Abstracts name (I) CAS RN [50864–67–0] PHYSICAL CHEMISTRY: M.f. BaS x COMMERCIALISATION: History Insecticide and fungicide introduced by Bayer AG. PRODUCTS: Discontinued products ‘Florbario’* (Sariaf); ‘Solbar’* (Bayer); ‘Tiobar’* (Farmoplant). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: EC Classifcation barium salts (with exceptions) are Xn; R20/22 (concentration- dependent) 34 The Pesticide Manual Sixteenth Edition © BCPC 2012 Bayer 22/190 Bayer 22/190 Insecticide IRAC 1B NOMENCLATURE: IUPAC name O-3-chloro-4-nitrophenyl O,O-dimethyl phosphorothioate Chemical Abstracts name O-(3-chloro-4-nitrophenyl) O,O-dimethyl phosphorothioate Other names chlorthion CAS RN [500–28–7] EC no 207–902–5 Development codes Bayer 22/190 Smiles code COP(=S)(OC)Oc1ccc([N+](=O)[O-])c(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 297.7 M.f. C 8 H 9 ClNO 5 PS M.p. 21 °C B.p. 136 °C /0.3 mbar; 112 °C /0.05 mbar V.p. 5.5 × 10 –1 mPa (20 °C) Henry 4.09 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.433 (4–20 °C) Solubility In water 40 mg/l (20 °C). Readily soluble in common organic solvents with the exception of mineral oils. Stability Rapidly hydrolysed in alkaline media, more slowly in the presence of acids. COMMERCIALISATION: History Insecticide introduced by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Insecticide with contact, stomach, and respiratory action. Uses Insecticidal control of aphids and sucking and biting insects in general in fruit, vine, and feld cultivation and forestry, especially control of the mangold fy and sawfy. Phytotoxicity Phytotoxic to a few varieties of apple (e.g. McIntosh). Formulation types WP; DP . PRODUCTS: Discontinued products ‘Chlorthion’* (Bayer). ANALYSIS: Product by extraction with ether or petroluem ether, washing with 1% sodium carbonate solution, reduction of the nitro group with zinc dust in glacial acetic acid/hydrochloric acid (9:1), and titration of the amine with sodium nitrite and iodine-starch (WHO Specifcations for Pesticide, 2nd edn, Geneva, 1961). Residues: depending on the moisture content of the sample, extraction with either acetone or chloroform, clean-up by liquid-liquid extraction or column chromatography, and gc determination with ECD (Man. Pestic. Residue Anal.,22). For colorimetric determination see Anal. Methods Pestic. Plant Growth Regul., 2,78, and for gc with ECD see Anal. Methods Pestic. Plant Growth Regul. 1972, 6, 322–324. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 4 (1965). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 625–1500 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 1500–4500 mg/kg. NOEL Administration of 10, 20, and 50 mg/kg diet for Supplementary Entries – Extended Bayer 32394 35 120 d produces no histopathological changes, apart from cholinesterase inhibition at ≥10 mg/kg. ADI/RfD (JMPR) No ADI [1965] EC Classifcation Xn; R20/21/22| N; R50, R53| concn. dep. ECOTOXICOLOGY: Fish Toxic to fsh and animals of fsh diet. Bees Toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Rapidly hydrolysed to dimethyl thiophosphate and 3-chloro-4- nitrophenol. To a limited extent, there is oxidation to the phosphate and hydrolysis to phosphoric acid and 3-chloronitrophenol. Bayer 22408 Insecticide IRAC 1B NOMENCLATURE: IUPAC name O,O-diethyl naphthalene-1,8-dicarboximido-oxyphosphonothioate; O,O-diethyl naphthalimido-oxyphosphonothioate; N-diethoxyphosphinothioyl= oxynaphthalene-1,8-dicarboximide Chemical Abstracts name 2-[(diethoxyphosphinothioyl)oxy]-1H-benz[de]isoquinoline- 1,3(2H)-dione CAS RN [2668–92–0] Development codes Bayer 22408; S 125 Smiles code CCOP(=S)(OCC)ON1C(=O)c2cccc3cccc(C1=O)c23 PHYSICAL CHEMISTRY: Mol. wt. 365.3 M.f. C 16 H 16 NO 5 PS COMMERCIALISATION: History Insecticide, discovered by W. Lorenz, evaluated by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Details PM1, p. 159. Bayer 32394 Fungicide NOMENCLATURE: IUPAC name tris(1-dodecyl-3-methyl-2-phenylbenzimidazolium) hexacyanoferrate Chemical Abstracts name tris[1-dodecyl-3-methyl-2-phenyl-1H- benzimidazolium] hexakis(cyano-C)ferrate CAS RN [7276–58–6], formerly [64070–97–9] and [16071–89–9] Development codes Bayer 32394; B 169 Ferricyanide Smiles code CCCCCCCCCCCCn1c(c2ccccc2)[n+](C)c3ccccc13. CCCCCCCCCCCCn1c(c2ccccc2)[n+](C)c3ccccc13.CCCCCCCCCCCCn1c(c2ccccc2) [n+](C)c3ccccc13.N#C[Fe-3](C#N)(C#N)(C#N)(C#N)C#N 36 The Pesticide Manual Sixteenth Edition © BCPC 2012 bencarbazone PHYSICAL CHEMISTRY: Mol. wt. 1344.7 M.f. C 84 H 111 FeN 12 COMMERCIALISATION: History Fungicide introduced by Bayer AG. APPLICATIONS: Mode of action Protective fungicide. PRODUCTS: Discontinued products ‘Fungilon’* (Bayer). Details PM2, p. 213. bencarbazone Herbicide NOMENCLATURE: Common name bencarbazone (BSI, E-ISO, (f) F-ISO) IUPAC name 4-[4,5-dihydro-4-methyl-5-oxo-3-(trifuoromethyl)-1H-1,2,4-triazol-1-yl]-2- [(ethylsulfonyl)amino]-5-fuorobenzenecarbothioamide Chemical Abstracts name 4-[4,5-dihydro-4-methyl-5-oxo-3-(trifuoromethyl)-1H-1,2,4- triazol-1-yl]-2-[(ethylsulfonyl)amino]-5-fuorobenzenecarbothioamide CAS RN [173980–17–1] Development codes TM-435; HWH 4991 PHYSICAL CHEMISTRY: Mol. wt. 427.4 M.f. C 13 H 13 F 4 N 5 O 3 S 2 Form Yellowish-grey powder. M.p. 202 °C K ow logP = 0.179 (pH 7.5) Solubility In water 0.105 g/l (pH 7). Stability Hydrolysis DT 50 >500 h (pH 4), 241 h (pH 7), 174 h (pH 9) (all at 50 °C). COMMERCIALISATION: History Herbicide discovered by Bayer CropScience; licensed to Tomen Agro (later Arysta LifeScience Corporation) in 2001. APPLICATIONS: Uses Evaluated for post-emergence control of broad-leaved weeds in maize and cereals. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >2500 mg/kg. Skin and eye Not a skin or eye irritant. Is a skin sensitiser (guinea pigs). Inhalation LC 50 (4 h) for rats >5045 mg/l. NOEL (13 w) for dogs 6 mg/kg. C NH 2 S F NHSO 2 CH 2 CH 3 N N N CF 3 O CH 3 Supplementary Entries – Extended benodanil 37 ECOTOXICOLOGY: Birds LD 50 (14 d) for bobwhite quail >2000 mg/kg daily. Fish LC 50 (96 h, static) for trout >100 mg/l. Daphnia EC 50 (48 h, static) >10 mg/l. Algae IC50 (72 h, static) for Selenastrum capricornutum 2 mg/l. Worms LC 50 (14 d) for earthworms >1000 mg/kg dry soil. benclothiaz Nematicide NOMENCLATURE: Common name benclothiaze ((m) F-ISO); benclothiaz (BSI, E-ISO) IUPAC name 7-chloro-1,2-benzothiazole Chemical Abstracts name 7-chloro-1,2-benzisothiazole CAS RN [89583–90–4] Development codes CGA 235 860 PHYSICAL CHEMISTRY: Mol. wt. 169.6 M.f. C 7 H 4 ClNS COMMERCIALISATION: History Nematicide evaluated by Novartis AG. benodanil Fungicide FRAC 7, C2 NOMENCLATURE: Common name benodanil (BSI, E-ISO, (m) F-ISO) IUPAC name 2-iodobenzanilide Chemical Abstracts name 2-iodo-N-phenylbenzamide CAS RN [15310–01–7] Development codes BAS 3170F (BASF) Smiles code Ic1ccccc1C(=O)Nc2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 323.1 M.f. C 13 H 10 INO Form Colourless crystals. M.p. 137 °C V.p. <0.010 mPa (20 °C) Henry <1.6 × 10 –4 Pa m 3 mol –1 (20 °C, calc.) Solubility In water 20 mg/l (20 °C). In acetone 401, ethyl acetate 120, ethanol 93, chloroform 77 (all in g/kg, 20 °C). Stability Stable ≤50 °C; no hydrolysis (20 °C) at pH 1 or pH 13. N S Cl C I O N H 38 The Pesticide Manual Sixteenth Edition © BCPC 2012 benquinox COMMERCIALISATION: History Fungicide reported by E. H. Pommer et al., at the 39th Deutsche Pfanzenschutztagung, Stuttgart, 1973 and by F. Löcher et al. (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1974, 39, 1079). Introduced by BASF AG. APPLICATIONS: Biochemistry SDHI: inhibits mitochondrial function by disrupting complex II (succinate dehydrogenase) in the respiratory electron transport chain. Mode of action Systemic and contact fungicide with protective and curative action. Uses Control of rust diseases of cereals, coffee, vegetables, and ornamentals; rust and fairy rings on turf; Rhizoctonia spp. on cotton, potatoes, cereals, rice, soya beans, ornamentals, vegetables, tobacco, and turf; and Typhula incarnata in cereals. Formulation types WP. PRODUCTS: Discontinued products ‘Calirus’* (BASF). ANALYSIS: Product by hplc. Residues by glc with ECD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and guinea pigs >6400 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Non-irritating to skin and eyes (rabbits). NOEL (90 d) for rats >100 mg/kg diet. Toxicity Class WHO (a.i.) U EPA (formulation) IV ECOTOXICOLOGY: Fish LC 50 (96 h) for trout 6.4 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Soil/Environment In loamy and humous sandy soils DT 50 c. 3–4 weeks. Details PM8, Entry 00710. benquinox Fungicide NOMENCLATURE: Common name tserenox (USSR); benquinox (BSI, E-ISO, (m) F-ISO) IUPAC name 2′-(4-hydroxyiminocyclohexa-2,5-dienylidene)benzohydrazide; 1,4-benzoquinone 1-benzoylhydrazone 4-oxime Chemical Abstracts name benzoic acid [4-(hydroxyimino)-2,5-cyclohexadien-1-ylidene]hydrazide Other names COBH CAS RN [495–73–8] EC no 207–807–9 Development codes Bayer 15 080 Smiles code ON=C1C=CC(=NNC(=O)c2ccccc2)C=C1 PHYSICAL CHEMISTRY: Mol. wt. 241.3 M.f. C 13 H 11 N 3 O 2 Form Yellow-brown crystals. M.p. 195 °C (decomp.) Supplementary Entries – Extended bentaluron 39 V.p. Non-volatile Solubility In water 5 mg/l (room temperature). Dissolves readily in aqueous alkalis with the formation of salts. Soluble in common organic solvents, readily soluble in formamide. Stability Very stable under normal conditions. Hydrolysed by strong acids and alkalis. COMMERCIALISATION: History Fungicide reported by P. E. Frohberger (Phytopath. Z., 1956, 37, 427). Introduced by Bayer AG. APPLICATIONS: Uses Fungicidal dressing to protect seeds and seedlings from soil fungi. Not used against cereal seed-borne diseases. Phytotoxicity Should not be used as a leaf fungicide. PRODUCTS: Discontinued products ‘Ceredon’* (Bayer); ‘Cereline’* (Bayer); Discontinued mixtures ‘Ceredon T’* (+ thiram) (Bayer); ‘Rhizoctol combi’* (+ methylarsenic sulfde) (Bayer); ‘Rhizoctol slurry’* (+ methylarsenic sulfde) (Bayer); ‘Tillantox’* (+ phenylmercury chloride) (Bayer). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for ratsc. 100 mg/kg. Toxicity Class WHO (a.i.) O EC Classifcation T; R25| Xn; R21 ECOTOXICOLOGY: Fish Toxic to fsh. LC 50 (48 h) for carp 0.048 mg/l. Bees Not known; irrelevant as regards the seed dressing agent. Details PM4, p. 35. bentaluron Fungicide NOMENCLATURE: Common name bentaluron (BSI, E-ISO, (m) F-ISO) IUPAC name 1-(1,3-benzothiazol- 2-yl)-3-isopropylurea; 1-benzothiazol-2-yl-3-isopropylurea Chemical Abstracts name N-2-benzothiazolyl-N′-(1-methylethyl)urea CAS RN [28956–64–1] Development codes CGA 18 734 Smiles code CC(C)NC(=O)Nc1nc2ccccc2s1 PHYSICAL CHEMISTRY: Mol. wt. 235.3 M.f. C 11 H 13 N 3 OS COMMERCIALISATION: History Fungicide evaluated by Ciba AG (later Ciba-Geigy AG). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. 40 The Pesticide Manual Sixteenth Edition © BCPC 2012 benzamorf benzadox; benzadox-ammonium Herbicide NOMENCLATURE: Common name benzadox (BSI, ANSI, WSSA) IUPAC name benzamido-oxyacetic acid Chemical Abstracts name [(benzoylamino)oxy]acetic acid CAS RN [5251–93–4] benzadox Development codes MC 0035 (Murphy); S 6173 (Gulf) Smiles code benzadox:OC(=O)CONC(=O)c1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 195.2; (ammonium salt 212.2) M.f. C 9 H 9 NO 4 ; (ammonium salt C 9 H 12 N 2 O 4 ) COMMERCIALISATION: History Herbicidal activity reported (Farm Chem., 1967, 130, 86). Introduced by Gulf Oil Corp. and by Murphy Chemical Co. (later DowElanco). PRODUCTS: Discontinued products ‘Topcide’* (Gulf). Details PM4, p. 38. benzamacril; benzamacril-isobutyl Fungicide NOMENCLATURE: Common name benzamacril (BSI, E-ISO, (m) F-ISO) IUPAC name 3-[benzyl(methyl)amino]-2-cyanoacrylic acid; 2-cyano-3-(N- methylbenzylamino)acrylic acid Chemical Abstracts name 2-cyano-3-[methyl(phenyl)amino]-2-propenoic acid CAS RN [88107–27–1] benzamacril-isobutyl; [127087–86–9] benzamacril Smiles code benzamacril-isobutyl:CC(C)COC(=O)C(=CN(C)Cc1ccccc1)C#N PHYSICAL CHEMISTRY: Mol. wt. 216.2; (isobutyl ester 272.4) M.f. C 12 H 12 N 2 O 2 ; (isobutyl ester C 16 H 20 N 2 O 2 ) COMMERCIALISATION: History Fungicide evaluated by FBC Limited (later Schering Agriculture). benzamorf Fungicide NOMENCLATURE: Common name benzamorf (BSI, E-ISO); benzamorphe ((m) F-ISO) IUPAC name morpholinium 4-dodecylbenzenesulfonate Supplementary Entries – Extended benzfendizone 41 Chemical Abstracts name 4-dodecylbenzenesulfonic acid compound with morpholine (1:1) CAS RN [12068–08–5] Development codes BAS 276F (BASF) Smiles code CCCCCCCCCCCCc1ccc(cc1)S(=O)(=O)[O-].C1COCC[NH2+]1 PHYSICAL CHEMISTRY: Mol. wt. 413.6 M.f. C 22 H 39 NO 4 S COMMERCIALISATION: History Fungicide introduced by BASF AG. APPLICATIONS: Mode of action Lipophilic fungicide. benzfendizone Herbicide HRAC E WSSA 14; pyrimidindione NOMENCLATURE: Common name benzfendizone (BSI, E-ISO, (f) F-ISO) IUPAC name methyl 2-{5-ethyl-2-[4-(1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4- trifuoromethylpyrimidin-1-yl)phenoxymethyl]phenoxy}propionate Chemical Abstracts name methyl 2-[2-[[4-[3,6-dihydro-3-methyl-2,6-dioxo-4- (trifuoromethyl)-1(2H)-pyrimidinyl]phenoxy]methyl]-5-ethylphenoxy]propanoate CAS RN [158755–95–4] Development codes FMC 143686; F3686 Smiles code CCc1ccc(COc2ccc(cc2)n3c(=O)cc(n(C)c3=O)C(F)(F)F)c(OC(C)C(=O)OC)c1 PHYSICAL CHEMISTRY: Mol. wt. 506.5 M.f. C 25 H 25 F 3 N 2 O 6 COMMERCIALISATION: History Herbicide evaluated by FMC. APPLICATIONS: Biochemistry Inhibitor of protoporphyrinogen oxidase. Uses Evaluated for post- emergence control of grass and broad-leaved weeds in orchards and no-till situations; also as a cotton defoliant and potato desiccant. Details PM14, Entry 70. N N CH 3 CH 2 O O O O CH 3 CF 3 CH 3 CH 3 O 2 C 42 The Pesticide Manual Sixteenth Edition © BCPC 2012 benzofuor benzipram Herbicide NOMENCLATURE: Common name benzipram (BSI, E-ISO, ANSI, WSSA); benziprame ((m) F-ISO) IUPAC name N-benzyl-N-isopropyl-3,5-dimethylbenzamide Chemical Abstracts name 3,5-dimethyl-N-(1-methylethyl)-N-(phenylmethyl)benzamide CAS RN [35256–86–1] Development codes S-18 510 Smiles code CC(C)N(Cc1ccccc1)C(=O)c2cc(C)cc(C)c2 PHYSICAL CHEMISTRY: Mol. wt. 281.4 M.f. C 19 H 23 NO COMMERCIALISATION: History Herbicide introduced by Gulf Oil Corp. 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone Insecticide synergist NOMENCLATURE: IUPAC name 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone Chemical Abstracts name 5-(5-benzo-1,3-dioxolyl)-3-hexyl-2-cyclohexen-1-one Other names piperonyl cyclonene CAS RN [8066–12–4] PHYSICAL CHEMISTRY: Mol. wt. 300.4 M.f. C 19 H 24 O 3 COMMERCIALISATION: History Synergist for insecticides. benzofuor Herbicide NOMENCLATURE: Common name benzofuor (BSI, ANSI, WSSA, E-ISO, (m) F-ISO) IUPAC name 4′-ethylthio-2′-(trifuoromethyl)methanesulfonanilide; 4′-ethylthio-α′,α′,α′- trifuoromethanesulfon-o-toluidide Chemical Abstracts name N-[4-(ethylthio)-2-(trifuoromethyl)phenyl] methanesulfonamide CAS RN [68672–17–3] Development codes MBR 18 337 Smiles code CCSc1ccc(NS(=O)(=O)C)c(c1)C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 299.3 M.f. C 10 H 12 F 3 NO 2 S 2 COMMERCIALISATION: History Herbicide and plant growth regulator introduced by 3M Company. Supplementary Entries – Extended benzoylprop; benzoylprop-ethyl 43 benzoylprop; benzoylprop-ethyl Herbicide NOMENCLATURE: Common name benzoylprop (BSI, E-ISO, (m) F-ISO, WSSA) IUPAC name N-benzoyl-N-(3,4-dichlorophenyl)-DL-alanine (I) Chemical Abstracts name (I) CAS RN [22212–55–1] benzoylprop-ethyl; [22212–56– 2] benzoylprop EC no 244–845–5 benzoylprop-ethyl Development codes WL 17 731 (ester) PHYSICAL CHEMISTRY: Composition Tech. is ≥93%. Mol. wt. 338.2; (ethyl ester 366.2) M.f. C 16 H 13 Cl 2 NO 3 ; ethyl ester C 18 H 17 Cl 2 NO 3 Form Tech. benzoylprop-ethyl is an off-white crystalline powder. M.p. 70–71 °C (ester) V.p. 0.0047 mPa (20 °C, ester) Solubility In water c. 20 mg/l (25 °C, ester). In acetone 700–750, ‘Shellsol A’ 250–300 (both g/l, 25 °C, for ester). Stability Stable photochemically, and hydrolytically over at least the range pH 3 to pH 6. COMMERCIALISATION: History Benzoylprop-ethyl is a herbicide reported by T. Chapman et al. (Symp. New. Herbic., 3rd, 1969, p. 40). Introduced by Shell Research Ltd. Patents GB 1164160 APPLICATIONS: Mode of action Selective herbicide Uses Applied at 1.0–1.5 kg/ha to wheat, it gives an 85–95% control of wild oat (Avena barbata, A. fatua, A. ludoviciana, A. sterilis). Field beans, oilseed rape and culinary mustard may also be safely treated. Crop competition ensures the effective control of wild oat, the stem elongation of which is inhibited (B. Jeffcoat & W. N. Harries, Pestic. Sci., 1973, 4, 891). Formulation types EC. PRODUCTS: Discontinued products ‘Suffx’* (Shell). ANALYSIS: Product analysis (ester) by glc (CIPAC Handbook, 1983, 1B, 1732) or by i.r. spectroscopy. Residues determined by glc with ECD (A. N. Wright & B. L. Mathews, Pestic. Sci., 1976, 7, 339). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1555, for mice 716 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg. NOEL In 90 d feeding trials, no change of toxicological signifcance in rats receiving 1000 mg/kg diet or dogs 300 mg/kg diet. Toxicity Class WHO (a.i.) III (for ethyl ester) EC Classifcation Xn; R22| N; R50, R53 (for DL-benzoylprop-ethyl) ENVIRONMENTAL FATE: The fate of the compound in plants, soils and animals has been reported (K. I. Beynon et al., 44 The Pesticide Manual Sixteenth Edition © BCPC 2012 benzthiazuron Pestic. Sci., 1974, 5, 429, 443, 451; J. V. Crayford et al., ibid., 1976, 7, 559). Details PM8, Entry 00850. benzthiazuron Herbicide NOMENCLATURE: Common name benzthiazuron (BSI, E-ISO, (m) F-ISO) IUPAC name 1-(1,3-benzothiazol-2-yl)-3-methylurea; 1-benzothiazol-2-yl-3-methylurea Chemical Abstracts name N-2-benzothiazolyl-N′-methylurea CAS RN [1929–88–0] EC no 217–685–9 Development codes Bayer 60 618 Smiles code CNC(=O)Nc1nc2ccccc2s1 PHYSICAL CHEMISTRY: Mol. wt. 207.3 M.f. C 9 H 9 N 3 OS Form Colourless powder. M.p. Decomposes (without melting) at 305-313 °C V.p. 1.3 mPa (92 °C, extrapolated) Solubility In water 15 mg/l (20 °C). In organic solvents such as acetone, chlorobenzene, DMF, xylene, isobutanol 5–10 mg/l; dichloromethane 3, toluene 1, isopropanol 4 (all in g/l, 20 °C). Stability Hydrolysed by strong acids and alkalis. COMMERCIALISATION: History Herbicide reported by H. Hack (International Meeting on Selective Weed Control in Sugar Beet Crops, Marly-le-Roi, 9–10 March 1967). Introduced in the Netherlands (1967) by Bayer AG. Patents BE 647740; GB 1004469 APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Interferes with cellular division at the level of RNA biosynthesis, and inhibits photosynthesis. Mode of action Selective herbicide, absorbed mainly by the roots. Uses Pre-emergence control of many germinating annual broad-leaved weeds in sugar beet, fodder beet, and spinach at 3.2–6.4 kg/ha. Formulation types WP. Compatibility Incompatible with quintozene and disulfoton. PRODUCTS: Discontinued products ‘Gatnon’* (Bayer). ANALYSIS: Product analysis by i.r. spectroscopy. Residues determined by uv spectroscopy (H. J. Jarczyk & K. Vogeler, Pfanz.-Nachr. Bayer (Engl. Ed.), 1967, 20, 575). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. N S NHCONHCH 3 Supplementary Entries – Extended binapacryl 45 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats >2500, male mice >1000, male dogs >1000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >500 mg/kg. Irritating to eyes; non- irritating to skin. NOEL (90 d) for rats 1000 mg/kg. In 60 d feeding trials, rats receiving 130 mg/kg daily showed no ill-effects. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22 ECOTOXICOLOGY: Fish Non-toxic to fsh. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 c. 10–12 weeks. Details PM9, Entry 0860. bethoxazin Algicide, fungicide NOMENCLATURE: Common name bethoxazine ((f) F-ISO); bethoxazin (BSI, E-ISO (not Japan)) IUPAC name 3-benzo[b]thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide Chemical Abstracts name 3-benzo[b]thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide CAS RN [163269–30–5] EC no 431–030–6 Development codes R 102622 Smiles code O=S1C(C2=CC3=CC=CC=C3S2)=NOCC1 PHYSICAL CHEMISTRY: Mol. wt. 251.3 M.f. C 11 H 9 NO 2 S 2 COMMERCIALISATION: Manufacturers Janssen binapacryl Acaricide, fungicide FRAC 29, C5; dinitrophenyl crotonate NOMENCLATURE: Common name binapacryl (BSI, E-ISO, (m) F-ISO, ANSI, ESA, JMAF) IUPAC name 2-sec-butyl-4,6-dinitrophenyl 3-methylbut-2-enoate Chemical Abstracts name 2-(1-methylpropyl)-4,6-dinitrophenyl 3-methyl-2- butenoate CAS RN [485–31–4] EC no 207–612–9 Development codes Hoe 02 784 Smiles code CCC(C)c1cc(cc([N+](=O)[O-])c1OC(=O)C=C(C)C)[N+](=O)[O-] S O N O S 46 The Pesticide Manual Sixteenth Edition © BCPC 2012 binapacryl PHYSICAL CHEMISTRY: Composition Tech. is ≥97%. Mol. wt. 322.3 M.f. C 15 H 18 N 2 O 6 Form Colourless crystalline powder. M.p. 66–67 °C; (tech., 65–69 °C) V.p. 13 mPa (60 °C) S.g./density 1.2 (20 °C); (tech. 1.25–1.28 (20 °C)) Solubility In water c. 1 mg/l (pH 5, 20 °C). In hexanec. 0.4, dichloromethane, ethyl acetate, toluene >500, methanolc. 21 (all in g/l, 20 °C). Stability Slowly decomposed by uv light; unstable in alkali and concentrated acids, and suffers slight hydrolysis on long contact with water. COMMERCIALISATION: History Acaricide and fungicide reported by L. Emmel & M. Czech (Anz. Schaedlingskd., 1960, 33, 145). Introduced by Hoechst AG. Patents GB 855736; DE 1099787 APPLICATIONS: Biochemistry Uncouples mitochondrial oxidative phosphorylation. Mode of action Non-systemic acaricide with contact action. Also a contact fungicide which acts by preventing germination of the conidia, and thus blocking reinfection. Uses Effective against powdery mildews; used mainly against all stages of spider mites and powdery mildews of apples, citrus, cotton, pears and top fruit at 25–50 g/100 l. Phytotoxicity Phytotoxic to blackcurrants, cyclamens, and to hydrangeas under glass. Formulation types EC; WP; SC. Compatibility Incompatible with alkalis. May be phytotoxic when mixed with some organophosphorus compounds. PRODUCTS: Discontinued products ‘Acricid’* (Hoechst); ‘Endosan’* (Hoechst); ‘Morocide’* (Hoechst); ‘Morrocid’* (Hoechst). ANALYSIS: Product analysis by hydrolysis to the parent phenol (dinoseb, q.v.) measured by colorimetry (D. S. Farrington et al., Analyst (London), 1983, 108, 353) or by titration with titanium trichloride. Residues determined by the former method (Pestic. Anal. Manual, 1979, I, 201-A, 201G; P. B. Baker & R. A. Hoodless, Analyst (London), 1973, 98, 172; R. W. Buxton & T. A. Mohr, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1967, 5, 235; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 314). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. II 46 (1985). ICSC.835 (1997). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEC as amended by 90/533/EEC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 150–225, male mice 1600–3200, female guinea pigs 300, dogs 450–640 mg/kg. Skin and eye Acute percutaneous LD 50 (acetone solution) for rabbits and mice 750 mg/kg. Slight eye irritant. NOEL In 2 y feeding trials, rats receiving 500 mg/kg diet and dogs receiving 50 mg/kg diet showed no ill-effects. ADI/RfD (JMPR) No ADI [1985]. Toxicity Class WHO (a.i.) II EC Classifcation R61| Xn; R21/22| N; R50, R53 PIC Yes. ECOTOXICOLOGY: Birds Acute oral LD 50 for chickens 800 mg/kg. Fish Max. tolerated dose for guppies 0.5, Supplementary Entries – Extended biopermethrin 47 carp 1.0, trout 2.0 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, hydrolysed to dinoseb (q.v.). Soil/Environment Duration of activity in soil is 15–25 d. Details PM8, Entry 00960. biopermethrin Insecticide IRAC 3 A single isomer, component of permethrin. NOMENCLATURE: Common name biopermé(thrine) ((f) F-ISO); biopermethrin (BSI, E-ISO) IUPAC name 3-phenoxybenzyl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethy lcyclopropanecarboxylate; 3-phenoxybenzyl (1R,3S)-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate Chemical Abstracts name (1R-trans)-(3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)- 2,2-dimethylcyclopropanecarboxylate; (3-phenoxyphenyl)methyl (1R,3S)-3-(2,2- dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate Other names permethrin-B; 1R-trans-permethrin CAS RN [51877–74–8] Development codes NRDC 147; RU 22090 Smiles code CC1(C)C(C=C(Cl)Cl)C1C(=O)OCc2cccc(Oc3ccccc3)c2 PHYSICAL CHEMISTRY: Mol. wt. 391.3 M.f. C 21 H 20 Cl 2 O 3 APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. ANALYSIS: Analysis of pyrethroids reviewed by E. Papadopoulou-Mourkidou in Comp. Anal. Profles. Permethrin isomers in drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: See A. J. Gray & D. M. Soderlund, Chapt. 5 in Insecticides. O CH 2 C CH CH 3 CH 3 Cl C O O Cl H H 48 The Pesticide Manual Sixteenth Edition © BCPC 2012 biphenyl biphenyl Fungicide FRAC 14, F3; aromatic hydrocarbon NOMENCLATURE: Common name biphenyl (BSI, E-ISO, F-ISO, accepted in lieu of common name) IUPAC name biphenyl Chemical Abstracts name 1,1′-biphenyl Other names diphenyl CAS RN [92–52–4] EC no 202–163–5 Smiles code c1ccc(cc1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 154.2 M.f. C 12 H 10 Form Colourless crystals. M.p. 70.5 °C B.p. 256 °C V.p. 4 Pa (20 °C) (CICAD) K ow logP = 3.88–4.04 (CICAD) S.g./ density 1.041 Solubility In water 4.45 mg/l (20 °C) (CICAD). Readily soluble in ethanol, diethyl ether, and other organic solvents. Stability Very stable in acidic and alkaline media. F.p. 106 °C COMMERCIALISATION: History Fungicidal activity against citrus-rotting fungi described by G. B. Ramsey et al. (Bot. Gaz., 1944, 106, 74). APPLICATIONS: Biochemistry Proposed mode of action is lipid peroxidation. Mode of action Fungistat which inhibits sporulation. Uses Used to impregnate citrus fruit wraps to prevent fungal attack. Formulation types Impregnated material. ANALYSIS: Residues determined by uv spectrometry (F. A. Gunther et al., Analyst (London), 1963, 88, 36; F. A. Gunther & D. E. Ott, ibid., 1966, 91, 475; S. Norman et al., J. Assoc. Off. Anal. Chem., 1966, 49, 590; AOAC Methods, 18th Ed., 968.25), by glc (H. Pyysalo et al., J. Chromatogr., 1979, 168, 512; Man. Pestic. Residue Anal., p. 6) or by hplc (J. E. Farrow et al., Analyst (London), 1977, 102, 752). See also Pestic. Anal. Man., I, 302. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 7 (1966), 9 (1967). ICSC.106 (1994). CICAD 6 (1999). EU Status (1107/2009) Not approved, 2004/129/EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3280, rabbits 2400, cats >2600 mg/kg. Depression of the central nervous system, paralysis, and convulsions have been observed in experimental animals. Inhalation Prolonged exposure of humans to vapour concentrations >0.005 mg/l air is considered dangerous (J. Deichmann et al., J. Ind. Hyg. Toxicol., 1947, 29, 1). NOEL NOAEL for rats 50 mg/kg b.w. daily (EPA IRIS). Supplementary Entries – Extended bis(2-chloroethyl) ether 49 ADI/RfD (JMPR) 0.125 mg/kg b.w. [1967]; (EPA) cRfD 0.05 mg/kg b.w. [1989]. Toxicity Class WHO (a.i.) U EPA (formulation) III EC Classifcation Xi; R36/37/38| N; R50, R53 ECOTOXICOLOGY: Fish LC 50 (96 h) for fsh 1.5–4.7 mg/l, with rainbow trout and fathead minnow the most sensitive species (CICAD). Daphnia LC 50 (8 h) 0.36 mg/l. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, metabolites identifed include 4-hydroxybiphenyl and other phenolic compounds (H. D. West et al., Arch. Biochem. Biophys., 1956, 60, 14–20). Plants Residues in fruit have been reviewed (A. Rajzman, Residue Rev., 1964, 8, 1; S. W. Souci & G. Maier-Haarländer, ibid., 1966, 16, 103). Details PM15, Entry 88. bis(2-chloroethyl) ether Insecticide NOMENCLATURE: Common name dichloroethyl ether (ESA) IUPAC name bis(2-chloroethyl) ether; di-(2-chloroethyl) ether Chemical Abstracts name 1,1′-oxybis[2-chloroethane] Other names DCEE CAS RN [111–44–4] EC no 203–870–1 Smiles code ClCCOCCCl PHYSICAL CHEMISTRY: Mol. wt. 143.0 M.f. C 4 H 8 Cl 2 O COMMERCIALISATION: History Insecticidal activity reported by R. C. Roark & R. T. Cotton (USDA Tech. Bull., 1929, No. 162); used to fumigate soil. APPLICATIONS: Mode of action Fumigant insecticide. PRODUCTS: Discontinued products ‘Chlorex’* (Union Carbide). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 201 (1998). ICSC.417 (2000). IARC 9 (1975); 71 (1999). MAMMALIAN TOXICOLOGY: IARC Class 3 EC Classifcation R40| T+; R26/27/28; concn. dep. Details PM4, p. 177. 50 The Pesticide Manual Sixteenth Edition © BCPC 2012 bis(methylmercury) sulfate 1,1-bis(4-chlorophenyl)-2-ethoxyethanol Acaricide NOMENCLATURE: IUPAC name 1,1-bis(4-chlorophenyl)-2-ethoxyethanol Chemical Abstracts name 4-chloro-α-(4-chlorophenyl)-α-(ethoxymethyl) benzenemethanol CAS RN [6012–83–5] Development codes Geigy 337; G 23 645 Smiles code CCOCC(O)(c1ccc(Cl)cc1)c2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 311.2 M.f. C 16 H 16 Cl 2 O 2 COMMERCIALISATION: History Acaricide introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). PRODUCTS: Discontinued products ‘Etoxinol’* (Ciba-Geigy). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg (Shibuya). bis(methylmercury) sulfate Fungicide NOMENCLATURE: IUPAC name bis(methylmercury) sulfate Chemical Abstracts name dimethyl-μ-sulfatodimercury CAS RN [3810–81–9] Smiles code C[Hg]OS(=O)(=O)O[Hg]C PHYSICAL CHEMISTRY: Mol. wt. 527.3 M.f. C 2 H 6 Hg 2 O 4 S COMMERCIALISATION: History Fungicide introduced by Bayer AG. PRODUCTS: Discontinued products ‘Aretannieuw’* (Bayer); ‘Cerewet’* (Bayer). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 9 (1967) EU Status (1107/2009) Alkyl mercury compounds considered to be outside the scope of the Directive; already banned, 79/117/EEC. MAMMALIAN TOXICOLOGY: IARC Class methylmercury compounds are classifed 2B EC Classifcation Not specifed, but organic mercury generally is assigned T+; R26/27/28| R33| N; R50, R53, concentration-dependent. PIC Not specifcally listed in the relevant DGD, but all mercury compounds are included in the PIC procedure. Details PM2, p. 47. Supplementary Entries – Extended bisthiosemi 51 bisthiosemi Rodenticide NOMENCLATURE: Common name bisthiosemi (JMAF) IUPAC name 1,1′-methylenedi(thiosemicarbazide) Chemical Abstracts name 2,2′-methylenebis(hydrazinecarbothioamide) CAS RN [39603–48–0] Development codes NK-15 561 Smiles code NC(=S)NNCNNC(=S)N PHYSICAL CHEMISTRY: Mol. wt. 194.3 M.f. C 3 H 10 N 6 S 2 Form Colourless crystals. M.p. Decomposes at 171–174 °C Solubility Almost insoluble in water and common organic solvents. Soluble in DMSO. Stability Decomposes slowly in water, and more rapidly in acidic or alkaline conditions. COMMERCIALISATION: History Rodenticide introduced by Nippon Kayaku Co., Ltd. Patents JP 50020126; GB 1351710; US 3826841 APPLICATIONS: Uses Control of Rattus norvegicus, Rattus rattus, and Microtus montebelli. Formulation types RB . PRODUCTS: Discontinued products ‘Kayanex’* (Nippon Kayaku). ANALYSIS: Product analysis by hydrolysis to thiosemicarbazide which is measured colorimetrically as a derivative. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice 30.4–50, guinea pigs 32–36, catsc. 150, dogs >1500 mg/kg. NOEL (90 d) for mice 100 mg/kg diet; for rats 50 mg/kg diet. Toxicity Class WHO (a.i.) II ECOTOXICOLOGY: Birds Acute oral LD 50 for chickens 120–150 mg/kg. Details PM9, Entry 8380. 52 The Pesticide Manual Sixteenth Edition © BCPC 2012 bis(tributyltin) oxide bis(tributyltin) oxide Fungicide NOMENCLATURE: IUPAC name bis(tributyltin) oxide Chemical Abstracts name hexabutyldistannoxane CAS RN [56–35–9] Smiles code CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC PHYSICAL CHEMISTRY: Mol. wt. 596.1 M.f. C 24 H 54 OSn 2 Form Colourless to pale yellow oil. M.p. –45 °C B.p. 180 °C /2 mmHg V.p. Negligible (20 °C) S.g./density 1.14 Solubility In water c. 100 mg/l; in sea water 60 mg/l (room temperature). Miscible with most organic solvents. Stability Stable to storage in dark, closed containers; forms bis(tributyltin) carbonate on exposure to air. COMMERCIALISATION: History Fungicide reported by J. G. A. Luijten & G. J. M. van der Kerk, Investigations Organotin. Introduced (1966) by M & T Chemicals Ltd. APPLICATIONS: Uses Mainly used as a toxicant in marine antifouling paints, to control Algae in industrial cooling water and as a wood preservative. Phytotoxic and unsuitable for use on growing crops or on cultivated soil. ANALYSIS: Product analysis by wet oxidation, reduction to tin(II) measured by titration with potassium iodate. Residues determined by hydrolysis to tin(II) salts estimated by colorimetry with dithiol (R. E. D. Clark, Analyst (London), 1936, 61, 242; 1937, 62, 661). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 116 (1990); a general review of tributyl tin compounds. PDS 65 (1985). ICSC.282 (1998). CICAD 14 (1999). EU Status (1107/2009) Not approved, as tributyltinoxyde, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 194 mg a.i. (as aqueous suspension)/kg (J. Elsea & O. E. Paynter, AMA Arch. Ind. Health, 1958, 18, 214). Skin and eye Absorbed by skin and may cause irritation. NOEL BMD10 (18 mo) immunotoxicity for rats 0.03 mg/kg b.w. daily (J. G. Vos, et al., 1990. Toxicol. Appl. Pharmacol. (1990) 105, 144–155, cited by EPA). ADI/RfD (EPA) cRfD 0.003 mg/kg b.w. [1997]. Water GV Excluded from GV derivation (U). Toxicity Class WHO (a.i.) Ib Details PM9, Entry 1180. Sn CH 3 (CH 2 ) 3 CH 3 (CH 2 ) 3 CH 3 (CH 2 ) 3 O Sn (CH 2 ) 3 CH 3 (CH 2 ) 3 CH 3 (CH 2 ) 3 CH 3 Supplementary Entries – Extended blasticidin-S; benzylaminobenzenesulfonate (BABS) salt 53 blasticidin-S; benzylaminobenzenesulfonate (BABS) salt Fungicide See also The Manual of Biocontrol Agents entry: 2:160 FRAC 23, D2; enopyranuronic acid antibiotic NOMENCLATURE: Common name blasticidin-S (JMAF) IUPAC name 1-(4-amino-1,2-dihydro-2-oxopyrimidin-1-yl)-4-[(S)-3-amino-5-(1- methylguanidino)valeramido]-1,2,3,4-tetradeoxy-β-D-erythro-hex-2-enopyranuronic acid Chemical Abstracts name (S)-4-[[3-amino-5-[(aminoiminomethyl)methylamino]-1- oxopentyl]amino]-1-[4-amino-2-oxo-1(2H)-pyrimidinyl]-1,2,3,4-tetradeoxy-β-D-erythro- hex-2-enopyranuronic acid (blasticidin); 4-[(phenylmethyl)amino]benzenesulfonic acid, compound with (S)-4-[[3-amino-5-[(aminoiminomethyl)methylamino]-1-oxopentyl] amino]-1-[4-amino-2-oxo-1(2H)-pyrimidinyl]-1,2,3,4-tetradeoxy-β-D-erythro-hex-2- enopyranuronic acid (BABS salt) Other names Bla-S CAS RN [2079–00–7] blasticidin, formerly [11002–92–9] and [12767–55–4]; [51775–28–1] BABS salt Development codes BcS-3 Smiles code CN(CC[C@@H](N)CC(=O)N[C@H]1/C=C\[C@H](OC1C(=O) O)n2ccc(N)nc2=O)C(=N)N; without stereochemistry:CN(CCC(N)CC(=O) NC1C=CC(OC1C(=O)O)n2ccc(N)nc2=O)C(=N)N; BABS salt, without stereochemistry:CN(CC[C@H](N)CC(=O)N[C@H]1C=C[C@@H](OC1C(=O)O) n2ccc(N)nc2=O)C(=N)N.OS(=O)(=O)c1ccc(NCc2ccccc2)cc1 N N NH 2 O O HO 2 C NH NH 2 C CH 2 CH 2 CH 2 CO H CH 3 N H 2 NC NH blasticidin S SO 3 H NH CH 2 benzylaminobenzenesulfonic acid 54 The Pesticide Manual Sixteenth Edition © BCPC 2012 blasticidin-S; benzylaminobenzenesulfonate (BABS) salt PHYSICAL CHEMISTRY: Mol. wt. 422.4; 685.6 (BABS salt) M.f. C 17 H 26 N 8 O 5 ; BABS salt C 30 H 39 N 9 O 8 S Form Colourless needles; (tech., light brown solid). M.p. 235-236 °C (decomp.) Solubility In water >30 g/l (20 °C). In acetic acid >30 g/l (20 °C). Practically insoluble in acetone, benzene, carbon tetrachloride, chloroform, cyclohexane, dioxane, ethanol, diethyl ether, ethyl acetate, methanol, pyridine, xylene. Stability Stable at pH 5–7; unstable at pH <4 and in alkali. Stable to light. Specifc rotation [α]11D +108.4° (c = 1.0 in water) pKa pKa1 2.4 (carboxyl), pKa2 4.6, pKa3 8.0, pKa4 >12.5 (three bases) COMMERCIALISATION: Production By the fermentation of Streptomyces griseochromogenes. History Antibiotic discovered by K. Fukunaga et al. (Bull. Agric. Chem. Soc. Jpn, 1955, 19, 18), its fungicidal properties reported by T. Misato et al. (Nippon Shokubutsu Byori Gakkaiho, 1959, 24, 302) and its structure elucidated by N. Otake (Agric. Biol. Chem., 1967, 30, 132). Its benzylaminobenzenesulfonate salt was introduced by Kaken Chemical Co., Ltd (later Kaken Pharmaceutical Co. Ltd), Kumiai Chemical Industry Co., Ltd, and Nihon Nohyaku Co., Ltd. APPLICATIONS: Biochemistry Protein synthesis inhibitor. Mode of action Contact fungicide with protective and curative action. Uses The BABS salt was used for control of rice blast (Pyricularia oryzae), by foliar application at 10–40 g/ha. Phytotoxicity Damage can be caused to alfalfa, aubergines, clover, potatoes, soya beans, tobacco, and tomatoes. Excessive application produces yellow spots on rice leaves. Formulated as the benzylaminobenzenesulfonate salt, to reduce phytotoxicity. Formulation types DP; EC; WP. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Bla-S’* (BABS salt) (Nihon Nohyaku). ANALYSIS: Product analysis by bioassay with Bacillus cereus IAM-1729. Residues determined by bioassay with Fulvia fulva ACI-1164. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 56.8, female rats 55.9, male mice 51.9, female mice 60.1 mg/kg. BABS salt, acute oral LD 50 for rats 53.3 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >500 mg/kg. Severe eye irritant. NOEL (2 y) for rats 1 mg/kg diet. Other Non-mutagenic in bacterial reversion tests. Toxicity Class WHO (a.i.) Ib EPA (formulation) II EC Classifcation T+; R28 ECOTOXICOLOGY: Fish LC 50 (48 h) for carp >40 mg/l. Daphnia LC 50 (3 h) for D. pulex >40 mg/l. ENVIRONMENTAL FATE: Animals Almost all of 3 H-blasticidin-S administered to mice was excreted in the urine and faeces within 24 h. Plants In rice plants, cytomycin and deaminohydroxy blasticidin-S were identifed as the main metabolites. Soil/Environment In soil, DT 50 <2 d (two soil types, o.c. 2.53%, 9.6%; moisture 42.6%, 87%, respectively; pH 6.0, 25 °C). Details PM13, Entry 85. Supplementary Entries – Extended 1-bromo-2-chloroethane 55 bromfenvinfos Insecticide IRAC 1B NOMENCLATURE: Common name bromfenvinfos (BSI, E-ISO, (m) F-ISO) IUPAC name 2-bromo-1-(2,4-dichlorophenyl)vinyl diethyl phosphate [(E)- to (Z)- ratio c. 1:18] Chemical Abstracts name 2-bromo-1-(2,4-dichlorophenyl)ethenyl diethyl phosphate CAS RN [33399–00–7] unstated stereochemistry; [58580–14–6] (E)- isomer; [58580–13– 5] (Z)- isomer Development codes IPO-62 Smiles code CCOP(=O)(OCC)OC(=CBr)c1ccc(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 404.0 M.f. C 12 H 14 BrCl 2 O 4 P COMMERCIALISATION: History Insecticide. APPLICATIONS: Biochemistry Cholinesterase inhibitor. 3-bromo-1-chloroprop-1-ene Insecticide NOMENCLATURE: IUPAC name 3-bromo-1-chloroprop-1-ene Chemical Abstracts name 3-bromo-1-chloro-1-propene CAS RN [3737–00–6] Development codes CBP-55 Smiles code CC(=CCl)Br PHYSICAL CHEMISTRY: Mol. wt. 155.4 M.f. C 3 H 4 BrCl COMMERCIALISATION: History Fumigant insecticide for soil introduced by Shell Development Co. APPLICATIONS: Uses Soil-fumigant insecticide 1-bromo-2-chloroethane Insecticide NOMENCLATURE: IUPAC name 1-bromo-2-chloroethane (I) Chemical Abstracts name (I) Other names ethylene chlorobromide; sym- chlorobromoethane CAS RN [107–04–0] Smiles code ClCCBr PHYSICAL CHEMISTRY: Mol. wt. 143.4 M.f. C 2 H 4 BrCl 56 The Pesticide Manual Sixteenth Edition © BCPC 2012 bromocyclen COMMERCIALISATION: History Insecticide used to fumigate soil, reported by M. W. Stone & F. B. Foley (J. Econ. Entomol., 1951, 44, 711). APPLICATIONS: Uses Soil-fumigant insecticide. Details PM4, p. 255. bromobonil Herbicide NOMENCLATURE: Common name bromobonil (BSI, E-ISO, (m) F-ISO) IUPAC name 2,6-dibromo-4-cyanophenyl tetrahydrofurfuryl carbonate Chemical Abstracts name 2,6-dibromo-4-cyanophenyl (tetrahydro-2-furanyl)methyl carbonate CAS RN [25671–46–9] unstated stereochemistry Smiles code Brc1cc(C#N)cc(Br)c1OC(=O)OCC2CCCO 2 PHYSICAL CHEMISTRY: Mol. wt. 405.1 M.f. C 13 H 11 Br 2 NO 4 COMMERCIALISATION: History Herbicide evaluated by Boehringer & Sohn (became Shell Agrar). bromocyclen Acaricide, insecticide, ixodicide NOMENCLATURE: Common name bromocyclen (BSI, E-ISO, BPC); bromocyclè(ne) ((m) F-ISO) IUPAC name 5-bromomethyl-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene; 5-bromomethyl-1,2,3,4,7,7-hexachloro-8,9,10-trinorborn-2-ene Chemical Abstracts name 5-(bromomethyl)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept- 2-ene CAS RN [1715–40–8] Smiles code ClC1=C(Cl)C2(Cl)C(CBr)CC1(Cl)C2(Cl)Cl PHYSICAL CHEMISTRY: Composition Tech. isc. 90%. Mol. wt. 393.8 M.f. C 8 H 5 BrCl 6 COMMERCIALISATION: History Veterinary insecticide and acaricide introduced by Hoechst AG. APPLICATIONS: Uses An insecticide and acaricide effective against ectoparasites such as Chorioptes, Cnemidocoptes, Notoedres, Otodectes, Psoroptes, Sarcoptes spp. and Cheyletiella parasitivorax on cats, cattle, dogs, horses, pigs, sheep and some birds. The host may be dusted, bathed or treated with an aerosol of bromocyclen. Formulation types AE; DP; WP. PRODUCTS: Discontinued products ‘Aludan’* (Hoechst); ‘Alugan’* (Hoechst); ‘Bromodan’* (Hoechst). Supplementary Entries – Extended bromofenoxim 57 TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 12 500 mg/kg. Toxicity Class WHO (a.i.) U Details PM8, Entry 01330. bromofenoxim Herbicide HRAC C3 WSSA 6 NOMENCLATURE: Common name bromofenoxim (BSI, E-ISO, WSSA); bromophé(noxime) ((f) F-ISO) IUPAC name 3,5-dibromo-4-hydroxybenzaldehyde 2,4-dinitrophenyloxime Chemical Abstracts name 3,5-dibromo-4-hydroxybenzaldehyde O-(2,4-dinitrophenyl) oxime CAS RN [13181–17–4], formerly [37273–85–1] EC no 236–129–6 Development codes C 9122 Smiles code Oc1c(Br)cc(C=NOc2ccc(cc2[N+](=O)[O-])[N+](=O)[O-])cc1Br PHYSICAL CHEMISTRY: Mol. wt. 461.0 M.f. C 13 H 7 Br 2 N 3 O 6 Form Cream-coloured crystals. M.p. 196–197 °C V.p. <1 × 10 –5 mPa (20 °C) K ow logP = 3.17 (pH 7.0) Henry 7.68 × 10 –6 Pa m 3 mol –1 (pH 3.8, 20 °C, calc.) S.g./density 2.15 (20 °C) Solubility In water 0.6 (pH 3.8), 9.0 (pH 10) (both in mg/l, 20 °C). In hexane 200, isopropanol 400, acetone 9900, n-octanol 200 (all in mg/l, 20 °C). Stability On hydrolysis, DT 50 (70 °C) 41.4 h (pH 1), 9.6 h (pH 5), 0.76 h (pH 9). pKa 5.46, weak acid COMMERCIALISATION: History Herbicide reported by D. H. Green et al. (Symp. New Herbic., 3rd, 1969, p. 77). Introduced by Ciba AG (later Novartis Crop Protection AG). Patents BE 675444; GB 1096037 Manufacturers Novartis APPLICATIONS: Biochemistry Generates bromoxynil (q.v.). Mode of action Selective herbicide with contact action. Absorbed by the leaves and stems, with some translocation. Uses Post- emergence control of many annual broad-leaved weeds in cereals, maize, grass-seed crops, grassland, and newly-seeded turf at rates in the range 1.0–2.5 kg/ha. Used in combination with other herbicides to extend the spectrum and period of activity. Formulation types WP; SC. HO Br Br CH O NO 2 N NO 2 58 The Pesticide Manual Sixteenth Edition © BCPC 2012 bromophos PRODUCTS: Discontinued products ‘Dicoprime’* (Ciba-Geigy); ‘Faneron’* (Novartis). ANALYSIS: Product analysis by hplc. Residues determined by hplc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1217, dogs >1000, mice 940 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3000 mg/kg. Mild skin and eye irritant (rabbits). Inhalation LC 50 (6 h) for rats >0.242 mg/l air. NOEL (2 y) for rats 100 mg/kg diet (3.8 mg/kg b.w. daily); (3 mo) for dogs 100 mg/kg diet (3 mg/kg b.w. daily), for mice 10 mg/kg diet (0.63 mg/kg b.w.. daily). ADI/RfD (BfR) 0.0015 mg/kg b.w. [1989]. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R22| N; R50, R53 ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for Japanese quail 5560, bobwhite quail 4000, mallard ducklings 2800 ppm. Fish LC 50 (96 h) for rainbow trout 0.18, carp 0.088 mg/l. Daphnia LC 50 (48 h) 1.2 mg/l. Algae EC 50 (96 h) for Algae 2.2 mg/l. Bees WP non-toxic; SC toxic. Worms LC 50 (14 d) for earthworms c. 1300 mg/kg. Other benefcial No effect on soil respiration, ammonifcation or nitrifcation. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, dinitrophenol and hydroxydibromobenzonitrile are formed, and are more slowly metabolised further and excreted in the urine; unchanged parent is the primary excretion product in the faeces. Plants In plants, 3,5-dibromo-4-hydroxybenzoic acid has been identifed as a metabolite. There is some conversion to bromoxynil. Soil/Environment Of low mobility with little or no persistence in the soil; DT 50 0.5–5 d. K oc 1100. Details PM11, Entry 86. bromophos Insecticide IRAC 1B NOMENCLATURE: Common name bromophos (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name O-4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate Br Cl Cl O P S OCH 3 OCH 3 Supplementary Entries – Extended bromophos 59 Chemical Abstracts name O-(4-bromo-2,5-dichlorophenyl) O,O- dimethyl phosphorothioate CAS RN [2104–96–3] EC no 218–277–3 Development codes S-1942 Smiles code COP(=S)(OC)Oc1cc(Cl)c(Br)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 366.0 M.f. C 8 H 8 BrCl 2 O 3 PS Form Yellow crystals. M.p. 53–54 °C B.p. 140–142 °C /0.01 mmHg V.p. 17 mPa (20 °C) Henry 8.89 Pa m 3 mol –1 (20 °C, calc.) Solubility In water 0.7 (20 °C), 40 (25 °C) (both in mg/l). In acetone 1090, dichloromethane 1120, xylene 900, methanol 100 (all in g/l, 20 °C). Stability Stable in solution up to pH 9 and in aqueous suspension, but hydrolysed in alkaline media. COMMERCIALISATION: History Insecticide reported by R. Immel & G. Geisthardt (Meded. Landbouwhogesch. Opzoekingsstn. Staat Gent, 1964, 29, 1242), and reviewed by D. Eichler (Residue Rev., 1972, 41, 65). Introduced by C. H. Boehringer Sohn/Cela GmbH (later Shell Agrar GmbH). Patents DE 1174104; GB 956343 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide with contact and stomach action. Uses Control of Diptera, Hemiptera, some Lepidoptera, Coleoptera, and other insects in fruit, vegetables, feld crops, ornamentals, and forestry. Important uses included control of cabbage root fies, carrot fies, onion fies, beet leaf miners, wheat bulb fies, frit fies, and bean seed fies. Also used for control of stored- product insect pests; in public health for control of fies, mosquitoes, etc.; as a household insecticide; for control of insects in animal houses; and as an animal dip. Phytotoxicity Phytotoxic to cotton and vines. Some varieties of pear, cabbage, and ornamentals, and glasshouse crops may be injured. Formulation types AE; DP; EC; WP; GR; KN; Seed treatment. Compatibility Not compatible with sulfur, organometallic compounds and alkaline pesticides. PRODUCTS: Discontinued products ‘Farel’* (Shell); ‘Nexion’* (Shell). ANALYSIS: Product by oxidation with bromide-bromate solution, and titration of the excess bromate with sodium thiosulfate (CIPAC Handbook, 1983, 1B, 1738; R. D. Weeren and D. Eichler Anal. Methods Pestic. Plant Growth Regul. 1978, 10, 33–34). Residues by glc with phosphorus- specifc FID (R. D. Weeren Anal. Methods Pestic. Plant Growth Regul. 1978, 10, 35–40; M. A. Luke et al., J. Assoc. Off. Anal. Chem. 1981, 64, 1187. Analyst (London), 1980, 105, 515); by fuorogenic labelling with dansyl chloride and tlc (S. Traore & J. J. Aaron Talanta 1981, 28(10), 765–767). See also Pestic. Anal. Man., I, 503. Determination of the halogenated phenol produced by hydrolysis can be used for both product and residue analysis. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Evaln. I 45 (1985); JMPR Evaln. 43 (1984). PDS 76 (1994). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. 60 The Pesticide Manual Sixteenth Edition © BCPC 2012 bromophos-ethyl MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3750–8000, mice 3311–5850, rabbits 720, guinea pigs 1500 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 2188 mg/kg. NOEL (2 y) for rats 0.63 mg/kg daily, for dogs 1.5 mg/kg daily. ADI/RfD (JMPR) 0.04 mg/kg b.w. [1977]. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R22| N; R50, R53| concn. dep. ECOTOXICOLOGY: Birds Acute oral LD 50 for hens 9700 mg/kg. Fish LC 50 for guppies 0.5, rainbow trout 0.05–0.5 mg/l. Bees LD 50 (oral) 18.8–19.6 mg/kg. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, >90% of the dose is eliminated within 24 h, principally in the urine. The pricipal metabolites are the desmethyl compound and the phenol (FAO/WHO datasheet 76 (1994)). Plants In tomato plants, the main metabolite is the phenol (M. Stiasni et al., J. Agr. Fd. Chem. (1969) 17, 1017, cited by FAO/WHO 28). Details PM8, Entry 01380. bromophos-ethyl Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name bromophos-ethyl (BSI, E-ISO, F-ISO, ESA) IUPAC name O-4-bromo-2,5-dichlorophenyl O,O-diethyl phosphorothioate Chemical Abstracts name O-(4-bromo-2,5-dichlorophenyl) O,O-diethyl phosphorothioate CAS RN [4824–78–6] EC no 225–399–0 Development codes S-2225 (Boehringer, Cela GmbH) Smiles code CCOP(=S)(OCC)Oc1cc(Cl)c(Br)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 394.1 M.f. C 10 H 12 BrCl 2 O 3 PS Form Colourless to pale yellow liquid. B.p. 122–123 °C /0.00l mmHg V.p. 6.1 mPa (30 °C) S.g./density 1.52–1.55 (20 °C) Solubility In water 0.14 mg/l (20 °C). Completely miscible with most common organic solvents. Stability Stable in aqueous suspension at pH <9; hydrolysed at higher pH. COMMERCIALISATION: History Insecticide reported by M. S. Mulla et al. (Mosq. News, 1964, 24, 312), and reviewed by D. Eichler (Residue Rev., 1972, 41, 65). Introduced by C. H. Boehringer Sohn/Cela GmbH (later Shell Agrar GmbH). Patents DE 1174104; GB 956343 Br Cl Cl O P S OCH 2 CH 3 OCH 2 CH 3 Supplementary Entries – Extended brompyrazon 61 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide and acaricide with contact and stomach action. Uses Control of Diptera, Hemiptera, some Lepidoptera, Coleoptera, some other insects, and mites in fruit, vegetables, feld crops, ornamentals, and forestry. Also used in public health for control of fies, mosquito larvae, etc.; for control of insects in animal houses; and as an animal ectoparasiticide. Formulation types EC; WP; GR; KN; UL . Compatibility Not compatible with sulfur and organometallic compounds. PRODUCTS: Discontinued products ‘Filariol’* (Celamerck); ‘Nexagan’* (Shell). ANALYSIS: Product by oxidation with bromide-bromate solution, and titration of the excess bromate with sodium thiosulfate (R. Weeren & D. Eichler Anal. Methods Pestic. Plant Growth Regul. 1978, 10, 33–34). Residues by glc with phosphorus-specifc FID (R. D. Weeren & D. Eichler Anal. Methods Pestic. Plant Growth Regul. 1978, 10, 35–40; D. C. Abbott et al., Pestic. Sci. 1970, 1, 10). Determination of the halogenated phenol produced by hydrolysis can be used for both product and residue analysis. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Evaln. 29 (1977). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 48, mice 210–550 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 100–600 mg/kg. Inhalation LC 50 (1.7 h) for rats 2.5 mg/l. NOEL (2 y) for rats 78 mg/kg daily, for dogs 0.26 mg/kg daily. ADI/RfD (JMPR) 0.003 mg/kg b.w. [1975]. Toxicity Class WHO (a.i.) Ib EPA (formulation) II EC Classifcation T; R25| Xn; R21| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for quail 200 mg/kg. Fish LC 50 (96 h) for guppies 0.14–0.24, rainbow trout >0.4 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, 85–90% of the dose is eliminated within 4 d in the faeces and urine. The principal metabolite is 4-bromo-2,5-dichlorophenol. Details PM8, Entry 01390. brompyrazon Herbicide NOMENCLATURE: Common name brompyrazon (BSI (from 1984), E-ISO); brompyrazone (BSI (before 1984), (f) F-ISO) 62 The Pesticide Manual Sixteenth Edition © BCPC 2012 bromuron IUPAC name 5-amino-4-bromo-2-phenylpyridazin-3(2H)-one Chemical Abstracts name 5-amino-4-bromo-2-phenyl-3(2H)-pyridazinone CAS RN [3042–84–0] Development codes BAS 2430H (BASF) Smiles code Nc1cnn(c2ccccc2)c(=O)c1Br PHYSICAL CHEMISTRY: Mol. wt. 266.1 M.f. C 10 H 8 BrN 3 O Form Yellowish crystalline powder. M.p. 223–224 °C Solubility In water 200 mg/l (20 °C). In benzene 0.3, chloroform 2, ethanol 11 (all in g/kg, 20 °C). COMMERCIALISATION: History Herbicide reported by A. Fischer (Weed Res., 1962, 2, 177). Introduced by BASF AG. APPLICATIONS: Mode of action Selective herbicide. Uses A mixture with isonoruron controls Alopecurus myosuroides, Apera spica-venti and annual broad-leaved weeds pre-em. or post-em. in cereals. PRODUCTS: Discontinued mixtures ‘Basanor’* (+ isonoruron) (BASF). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >6400 mg ‘Basanor’/kg. Skin and eye The formulation caused only slight reddening 24 h after application to the shaved skin of rabbits. ECOTOXICOLOGY: Fish LC 50 for guppies 10–20 mg/l. Details PM5, p. 55. bromuron Herbicide NOMENCLATURE: IUPAC name N′-(4-bromophenyl)-N-dimethylurea (I) Chemical Abstracts name (I) CAS RN [3408–97–7] Development codes FL 173 (Fahlberg-List) PHYSICAL CHEMISTRY: Mol. wt. 243.1 M.f. C 9 H 11 BrN 2 O Form Colourless crystals. M.p. 172–174 °C V.p. 0.5 mPa (25 °C) Henry 5 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.28 at 25 °C Solubility In water 0.237 g/l (22.5 °C). In acetone 76.4, benzene 3.1, chloroform 35.8, 1,2-dichloroethane 7.2, hexane 0.4 (all in g/kg, 25 °C). Stability Stable under normal conditions at pH 7. Decomposes in strong acids and alkalis. Stable to light. COMMERCIALISATION: Manufacturers Fahlberg-List APPLICATIONS: Biochemistry Photosynthesis inhibitor. Uses Pre-emergence control of annual weeds. Used, preferably in combination with other herbicides, in potatoes and vegetables. Formulation types WP Supplementary Entries – Extended BTS 44584 63 PRODUCTS: Discontinued products ‘Faluron’* (Fahlberg-List). ANALYSIS: Product and residue analysis by tlc (M. Koennig et al., Nachrichtenbl. Pfanzenschutz DDR 1987, 41, 55). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1920 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >20 000 mg/kg. Non-irritating to skin. NOEL (90 d) for rats 5 mg/kg daily. ECOTOXICOLOGY: Fish LC 50 (96 h) for guppies 112 mg/l; (48 h) for guppies 138 mg/l. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 c. 112–118 d. BTS 44584 Plant growth regulator NOMENCLATURE: IUPAC name dimethyl(4-piperidinocarbonyloxy-2,5-xylyl)sulfonium toluene-4-sulfonate Chemical Abstracts name [2,5-dimethyl-4-[(4-piperidinylcarbonyl)oxy] phenyl]dimethylsulfonium 4-methylbenzenesulfonate CAS RN [68721–60–8] Development codes BTS 44584 Smiles code C[S+](C)c1cc(C)c(OC(=O)N 2 CCCCC2) cc1C.Cc1ccc(cc1)S(=O)(=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 465.6 M.f. C 23 H 31 NO 5 S 2 COMMERCIALISATION: History Plant growth regulator reported by J. F. Garrod et al. (Monograph Brit. Plant Growth Regulator Group, 1980, No. 4, p. 67). Evaluated by Boots Co., Ltd (later Schering Agriculture). Patents GB 1593541. APPLICATIONS: Uses Retards growth of various crops, including beans, chrysanthemums, cotton, soya beans and sunfowers. Formulation types SP. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >400 mg/kg. Details PM7, Entry 4990. S + O O N S O O O - dimethyl(4-piperidinocarbonyloxy-2,5-xylyl)sulfonium toluene-4-sulfonate 64 The Pesticide Manual Sixteenth Edition © BCPC 2012 bufencarb bufencarb Insecticide NOMENCLATURE: Common name bufencarbe ((m) F-ISO); bufencarb (for a reaction product) (BSI, E-ISO, ANSI, ESA) IUPAC name of the main components are: (i) 3-(1-methylbutyl)phenyl methylcarbamate (I); and (ii) 3-(1-ethylpropyl)phenyl methylcarbamate (II) Chemical Abstracts name (I) and (II) CAS RN [8065–36–9] bufencarb; [2282–34–0] (i); [672–04–8] (ii) Development codes Ortho 5353 PHYSICAL CHEMISTRY: Composition Produced by the action of methyl isocyanate on a reaction mixture of alkylated phenols, tech. bufencarb comprisesc. 65% of a 3:1 mixture of (i) and (ii) and 35% of insecticidally-inactive related isomers (mainly the 2- and 4-alkyl analogues). Mol. wt. 221.3 M.f. C 13 H 19 NO 2 Form Tech. mixture is a yellow to amber coloured solid. M.p. 26– 39 °C (tech.) B.p. c. 125 °C /0.04 mmHg V.p. 4.0 mPa (30 °C) S.g./density 1.024 (26 °C, tech.) Solubility In water <50 mg/l (room temperature). Very soluble in methanol, xylene; less so in hexane. Stability Stable in acid or neutral solutions, but hydrolysis increases with pH or temperature. COMMERCIALISATION: History Insecticide introduced by Chevron Chemical Company LLC. Patents US 3062864, US 3062867 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Insecticide with contact and stomach action. Uses Insecticide, effective at 0.5–2.0 kg/ha against a range of soil- and foliage-inhabiting insects, particularly Chilo plejadellus, Crambus caliginosellus larvae, Dysmicoccus brevipes, Lissorhoptrus oryzophilus, Nephotettix nigropictus, rice planthoppers. Formulation types DP; EC; GR . PRODUCTS: Discontinued products ‘Bux’* (Chevron); ‘Bux Ten’* (Chevron). ANALYSIS: Product analysis is by glc (B. Tucker, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 179). Residues may be determined by glc (idem, ibid.) or by rplc (AOAC Methods, 18th Ed., 985.23). See also Pestic. Anal. Man., I, 401. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 87 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rabbits 680 mg/kg. Minimal eye irritation (rabbits). NOEL In 90 d feeding trials, no effect was noted with beagle dogs and albino rats receiving ≤500 mg/kg diet. Supplementary Entries – Extended buminafos 65 Toxicity Class WHO (a.i.) II EC Classifcation T; R24/25| N; R50, R53 ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for pheasants and ducks >27 000 mg/kg. Fish LC 50 (96 h) for goldfsh 0.56, catfsh 1.95, trout 0.064 mg/l. ENVIRONMENTAL FATE: Soil/Environment Degraded in soil. Details PM7, Entry 01450. buminafos Plant growth regulator NOMENCLATURE: Common name buminafos (BSI, E-ISO, (m) F-ISO) IUPAC name dibutyl 1-butylaminocyclohexylphosphonate Chemical Abstracts name dibutyl 1-(butylamino)cyclohexylphosphonate CAS RN [51249–05–9] Smiles code CCCCNC1(CCCCC1)P(=O)(OCCCC)OCCCC PHYSICAL CHEMISTRY: Mol. wt. 347.5 M.f. C 18 H 38 NO 3 P M.p. c. –25 °C B.p. 95–99 °C /1 mmHg V.p. c. 100 mPa (20 °C) Henry 2 × 10 –1 Pa m 3 mol –1 (20 °C, calc.) S.g./density 0.969 (20 °C) Solubility In water 170 mg/l (room temperature). Readily miscible with common organic solvents (e.g. acetone, methanol, xylene, etc.). Immiscible with diesel oil. Stability Hydrolysed by strong acids and alkalis. Aqueous hydrolysis DT 50 13 d (pH 6), 20 h (pH 8), 2.75 h (pH 11). COMMERCIALISATION: History Plant growth regulator evaluated by VEB Chemiekombinat Bitterfeld. Later marketed by Luxan B.V. APPLICATIONS: Mode of action Non-selective contact herbicide, absorbed by the leaves and roots. Uses Control of annual grass and broad-leaved weeds in vegetables, beet, ornamental plants and shrubs, strawberries, herbs, fruit-tree nurseries, and land to be used for horticulture. Also used for destruction of potato haulms; for cleaning and removal of side-shoots in hops; as a cotton defoliant; and as a desiccant for Leguminosae and seed crops of brassicas, spinach, onions, and beet. Formulation types EC. PRODUCTS: Discontinued products ‘Trakefon’* (Luxan); ‘Trakephon’* (Asepta). ANALYSIS: Product by nmr spectrophotometry. Residues by tlc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 7000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 66 The Pesticide Manual Sixteenth Edition © BCPC 2012 butathiofos 12 000–15 000, rabbits 5000–8000 mg/kg. Irritating to skin and eyes. NOEL (130 d) for rats 140 mg/kg daily. ECOTOXICOLOGY: Fish LC 50 (96 h) for guppies 7 mg/l. Bees Not hazardous to bees if used as directed. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, rapidly metabolised by dealkylation at the oxygen and nitrogen atoms, followed by deamination. Soil/Environment Soil DT 50 c. 8–11 d. butacarb Insecticide NOMENCLATURE: Common name butacarb (BSI, E-ISO); butacarbe ((m) F-ISO) IUPAC name 3,5-di-tert-butylphenyl methylcarbamate Chemical Abstracts name 3,5-bis(1,1-dimethylethyl)phenyl methylcarbamate CAS RN [2655–19–8] Development codes RD 14 639; BTS 14 639 Smiles code CNC(=O)Oc1cc(cc(c1)C(C)(C)C)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 263.4 M.f. C 16 H 25 NO 2 COMMERCIALISATION: History Acaricide reported by J. Fraser et al. (J. Sci. Food Agric., 1967, 18, 372), used as mixture with gamma-HCH against animal ectoparasites. Introduced by Boots Co., Ltd (later Schering Agrochemicals). APPLICATIONS: Biochemistry Cholinesterase inhibitor. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Details PM5, p. 59. butathiofos Insecticide P O O O S N N O-2-tert-butylpyrimidin-5-yl O,O-diethyl phosphorothioate Supplementary Entries – Extended butenachlor 67 IRAC 1B NOMENCLATURE: Common name butathiofos (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name O-2-tert-butylpyrimidin-5-yl O,O-diethyl phosphorothioate Chemical Abstracts name O-[2-(1,1-dimethylethyl)-5-pyrimidinyl] O,O-diethyl phosphorothioate CAS RN [90338–20–8] Development codes Dowco 429; XRD 429 Smiles code CCOP(=S)(OCC)Oc1cnc(nc1)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 304.4 M.f. C 12 H 21 N 2 O 3 PS Form Colourless oil. B.p. 290 °C V.p. 22 mPa (25 °C) K ow logP = 4 (pH 7) Solubility In water 19.4 mg/l (20 °C). In acetone, cyclohexanone, DMF, methanol, xylene >500, digol 98, propane-1,2-diol 58 (all in g/l, 20 °C). COMMERCIALISATION: History Insecticide evaluated by DowElanco. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses A pre-plant. treatment (c. 250 g/ha) controls Diabrotica spp. and other soil-dwelling pests in maize. Formulation types GR . PRODUCTS: Discontinued products ‘Butafos’* (Dow). ANALYSIS: Product and residue analysis by hplc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice 15, rats 3.2 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 12.6–25.2 mg/kg. NOEL (2 y) for rats 0.01 mg/kg daily. ECOTOXICOLOGY: Daphnia LC 50 0.30 mg/l. Bees Acute toxicity to honeybees 7.7 ng/bee. butenachlor Herbicide NOMENCLATURE: Common name buté(nachlore) ((m) F-ISO); butenachlor (BSI, E-ISO) IUPAC name (Z)-N-but-2-enyloxymethyl-2-chloro-2′,6′-diethylacetanilide CH 2 CH 3 N CH 2 CH 3 COCH 2 Cl CH 2 C C CH 3 H H CH 2 O 68 The Pesticide Manual Sixteenth Edition © BCPC 2012 buthidazole Chemical Abstracts name (Z)-2-chloro-N-[(2-butenyloxy)methyl]-N-(2,6- diethylphenyl)acetamide CAS RN [87310–56–3] Development codes KH-218 Smiles code CCc1cccc(CC)c1N(COCC=CC)C(=O)CCl PHYSICAL CHEMISTRY: Mol. wt. 309.8 M.f. C 17 H 24 ClNO 2 Form Light-yellow liquid. M.p. 12.9 °C B.p. 167 °C /399 Pa V.p. 0.93 mPa (25 °C) K ow logP = 3.51 (hplc method) Henry 1 × 10 –2 Pa m 3 mol –1 (calc.) S.g./density 1.0998 Solubility In water 29 mg/l (27 °C). Miscible with acetone, ethanol, ethyl acetate, and hexane. Stability Stable in acidic, neutral, and weakly alkaline media. Unstable in sunlight. COMMERCIALISATION: History Herbicide introduced by Agro-Kanesho Co., Ltd. Patents US 4798618; JP 1518580 Manufacturers Agro-Kanesho APPLICATIONS: Biochemistry Inhibits cell division by blocking protein synthesis. It is reported that chloroacetamides inhibit synthesis of very long chain fatty acids (J. Schmalfuss et al., Abstr. Meeting WSSA, Toronto, 40, 117–118, 2000; P. Böger, Abstr. III Int. Weed Control Congr., Brazil, 2000). Mode of action Selective herbicide, absorbed primarily by germinating shoots, and secondarily by roots, with translocation throughout the plant, giving higher concentrations in vegetative parts than in reproductive parts. Uses Pre-emergence control of most grass and some broad-leaved weeds, and many aquatic weeds, in both seeded and transplanted rice at 0.75–1.0 kg/ha. Formulation types GR . ANALYSIS: Product analysis by glc. Residues determined by glc with NPD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 1630, female rats 1875, male mice 6417, female mice 6220 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Slightly irritating to eyes and skin. Inhalation LC 50 (4 h) for rats 3.34 mg/l air. NOEL (90 d) for rats 20, dogs 25 mg/kg. Non-teratogenic and no reproductive effects evident. Toxicity Class WHO (a.i.) II ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail and mallard ducks >2000 mg/kg. Fish LC 50 (96 h) for mirror carp 0.48, Japanese killifsh 0.42 mg/l. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 2–5 d. Details PM10, Entry 90. buthidazole Herbicide NOMENCLATURE: Common name buthidazole (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name 3-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-4-hydroxy-1-methyl-2-imidazolidone Supplementary Entries – Extended buthiobate 69 Chemical Abstracts name 3-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-4-hydroxy- 1-methyl-2-imidazolidinone CAS RN [55511–98–3] Development codes Vel-5026 Smiles code CN1CC(O)N(C1=O)c2nnc(s2)C(C)(C)C PHYSICAL CHEMISTRY: Composition Tech. is ≥86%. Mol. wt. 256.3 M.f. C 10 H 16 N 4 O 2 S Form Colourless crystals; (tech. is a tan powder). M.p. 133–134 °C V.p. 0.0053 mPa (25 °C) Henry 2.09 × 10-7 Pa m 3 mol –1 (calc.) S.g./density 1.28 (25 °C) Solubility In water 6.5 g/kg (25 °C). In acetone 150, DMF 208, toluene 45, xylene, 10 (all in g/kg, 25 °C). Stability Decomposes at 237 °C; relatively resistant to uv degradation. COMMERCIALISATION: History Herbicide reported by R. F. Anderson (Proc. Int. Velsicol Symp., 8th, 1974). Introduced by Velsicol Chemical Corp. (later Sandoz AG). Patents US 3904640 APPLICATIONS: Mode of action Contact herbicide. Uses Residual pre- and post-emergence herbicide in industrial and non-crop areas at 4.5–6.5 kg/ha depending on rainfall. Used at lower rates against broad-leaved weeds and annual grasses in maize, pineapple and sugar cane. Formulation types GR; WP. PRODUCTS: Discontinued products ‘Ravage’* (Sandoz). ANALYSIS: Product analysis and soil residue determinations are by hplc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1575–2430 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >20 000 mg/kg. Non-irritant to skin and eyes (rabbits). Inhalation LC 50 (4 h) for rats >20.8 mg/l (dust). NOEL (2 y) for rats 300 mg/kg diet; liver tumours reported in mice at ≥1000 mg/kg diet. Not teratogenic in rabbits at 90 mg/kg daily. NOEL for rats (3 generations) 1500 mg/kg diet. Other Non-mutagenic to mammalian cells. Toxicity Class WHO (a.i.) III ENVIRONMENTAL FATE: Soil/Environment DT 50 >50 d. Details PM7, Entry 01530. buthiobate Fungicide NOMENCLATURE: Common name buthiobate (BSI, E-ISO, (m) F-ISO) IUPAC name butyl 4-tert-butylbenzyl N-(3-pyridyl)dithiocarbonimidate Chemical Abstracts name butyl [4-(1,1-dimethylethyl)phenyl]methyl 70 The Pesticide Manual Sixteenth Edition © BCPC 2012 buthiuron 3-pyridinylcarbonimidodithioate CAS RN [51308–54–4] Development codes S-1358 (Sumitomo Chemical) Smiles code CCCCSC(=Nc1cccnc1)SCc2ccc(cc2)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 372.6 M.f. C 21 H 28 N 2 S 2 Form Tech. is a red-brown viscous liquid. M.p. 31–33 °C (tech.) V.p. 0.06 mPa (20 °C) S.g./density 1.0865 (25 °C, tech.) Solubility In water 1 mg/l (25 °C). In methanol and xylene >1 kg/kg (23 °C). COMMERCIALISATION: History Fungicide reported by T. Kato et al. (Agric. Biol. Chem., 1975, 39, 169). Introduced by Sumitomo Chemical Co., Ltd. Patents GB 1335617; US 3832351 APPLICATIONS: Biochemistry Ergosterol biosynthesis inhibitor. Mode of action Fungicide with protective and curative action, and long persistence. Uses Fungicide with rain fastness. It was effective against powdery mildew on beans, fruit, ornamentals, vegetables and other crops. Applied at 15–250 mg/l. Phytotoxicity Some varieties of beans may be injured at high concentrations. Formulation types EC; WP. PRODUCTS: Discontinued products ‘Denmert’* (Sumitomo Chemical). ANALYSIS: Product analysis by glc (S. Irie et al., Nippon Nogei Kagaku Kaishi, 1977, 51, 331). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 4400, female rats 3200 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Not a skin or eye irritant (rabbits). Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks >10 000, bobwhite quail 21 800 mg/kg. Fish LC 50 (48 h) for carp 6.4 mg/l. Details PM8, Entry 01540. buthiuron Herbicide NOMENCLATURE: Common name buthiuron (BSI, E-ISO, (m) F-ISO) IUPAC name 1-(5-butylsulfonyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea Chemical Abstracts name N-[5-(butylsulfonyl)-1,3,4-thiadiazol-2-yl]-N,N′-dimethylurea CAS RN [30043–55–1] Development codes MET 1489 Smiles code CCCCS(=O)(=O)c1nnc(s1)N(C)C(=O)NC PHYSICAL CHEMISTRY: Mol. wt. 292.4 M.f. C 9 H 16 N 4 O 3 S 2 COMMERCIALISATION: History Herbicide evaluated by Bayer AG. Supplementary Entries – Extended butocarboxim 71 butocarboxim Acaricide, insecticide IRAC 1A; oxime carbamate NOMENCLATURE: Common name butocarboxim (BSI, E-ISO); butocarboxime ((f) F-ISO) IUPAC name 3-(methylthio)butanone O-methylcarbamoyloxime Chemical Abstracts name 3-(methylthio)-2-butanone O-[(methylamino)carbonyl]oxime CAS RN [34681–10–2] EC no 252–139–3 Development codes Co 755 (Wacker) Smiles code CNC(=O)ON=C(C)C(C)SC PHYSICAL CHEMISTRY: Composition Tech. grade is liquid and obtained as an 85% tech. concentrate in xylene containing the (E)- and (Z)- isomers in a ratio of 85–90:15–10. Mol. wt. 190.3 M.f. C 7 H 14 N 2 O 2 S Form Pale brown, viscous liquid (tech.). Crystalline at lower temperatures. M.p. 37 °C ((E)- isomer); ((Z)- isomer is an oil at room temperature) V.p. 10.6 mPa (20 °C) (tech., without residual xylene) K ow logP = 1.1 Henry 5.76 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.12 (20 °C) Solubility In water 35 g/l (20 °C). Completely miscible with aromatic hydrocarbons, esters, and ketones. Low solubility in aliphatic hydrocarbons (11 g/l) and carbon tetrachloride. Stability Stable at pH 5–7 (up to 50 °C), but hydrolysed by strong acids and alkalis. Stable to sunlight and oxygen. Thermally stable up to 100 °C. COMMERCIALISATION: History Insecticide reported by M. Vulic et al. (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1973, 38, 1175). Structure/activity of analogues discussed (T. A. Magee & L. E. Limpel, J. Agric. Food Chem., 1977, 25, 1376). Introduced by Wacker-Chemie GmbH. Patents DE 2036491; US 3816532; GB 1353202 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide with contact and stomach action. Absorbed by the leaves and roots. Uses Control of aphids, thrips, whitefies, mealybugs, and other sucking insects (with secondary action against spider mites) on fruit trees (including citrus), vegetables, cereals, cotton, hops, tobacco, and ornamentals (including ornamentals cultivated by hydroponics). Formulation types AE; EC; SL . (E)- (Z)- CH 3 C CH CH 3 N O C NH O CH 3 SCH 3 CH 3 C CH CH 3 N O C NH O CH 3 SCH 3 72 The Pesticide Manual Sixteenth Edition © BCPC 2012 butonate PRODUCTS: Discontinued products ‘Drawin’* (Wacker); ‘Hydrosekt’* (Luxan). ANALYSIS: Product analysis by i.r. spectrometry or by hplc. Residues of butocarboxim, its sulfoxide and sulfone (butoxycarboxim) determined by glc with TID. Details available from Wacker- Chemie GmbH. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. JMPR Evaln. I 48 (1986). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 153–215 mg/kg. Skin and eye Acute percutaneous LD 50 for albino rabbits 360 mg/kg. Irritating to eyes. Inhalation LC 50 (4 h) for rats 1 mg/l air. NOEL (2 y) for rats 100 mg/kg diet; (90 d) for dogs 100 mg/kg diet. No carcinogenic or mutagenic activity in routine tests at the highest dose (300 mg/kg diet) in rats during 2 y, nor any effect on fertility, growth rate or mortality. ADI/RfD (JMPR) No ADI [1985]; (BfR) 0.02 mg/kg b.w. [1990]. Other Not mutagenic in the Ames assay. Toxicity Class WHO (a.i.) Ib EPA (formulation) II EC Classifcation R10| T; R23/24/25| Xi; R36| N; R50, R53 ECOTOXICOLOGY: Birds LD 50 for mallard ducks 64 mg/kg. LC 50 (8 d) for Japanese quail 1180 mg/kg diet. Fish LC 50 (96 h) for rainbow trout 29 mg/l. LC 50 (24 h) for rainbow trout 35, goldfsh 55, guppies 70 mg/l. Daphnia LC 50 (24 h) 3.2–5.6 mg/l. Algae NOEL for Algae 62.5 mg/l. Bees Toxic to bees; LD 50 1 μg/bee. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, metabolised to butoxycarboxim, and excreted in the urine as butoxycarboxim and its degradation products. Plants In plants, degradation is the same as in soil. Soil/Environment In soil, the methylamine moiety is split off, and the sulfur atom is oxidised to sulfoxide and sulfone. DT 50 in soil 1–8 d; DT 50 for metabolites 16–44 d. Details PM15, Entry 110. butonate Insecticide IRAC 1B NOMENCLATURE: Common name butonate (BSI, E-ISO, (m) F-ISO); butilchlorofos* (former exception USSR) IUPAC name 2,2,2-trichloro-1-(dimethoxyphosphinoyl)ethyl butyrate Chemical Abstracts name 2,2,2-trichloro-1-(dimethoxyphosphinyl)ethyl butanoate CAS RN [126–22–7] Smiles code CCCC(=O)OC(C(Cl)(Cl)Cl)P(=O)(OC)OC Supplementary Entries – Extended butopyronoxyl 73 PHYSICAL CHEMISTRY: Mol. wt. 327.5 M.f. C 8 H 14 Cl 3 O 5 P COMMERCIALISATION: History Insecticide reported by B. W. Arthur & J. E. Casida (J. Agric. Food Chem., 1958, 6, 360). Introduced by Prentiss Drug & Chemical Co. APPLICATIONS: Biochemistry Cholinesterase inhibitor. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Details PM4, p. 61. butopyronoxyl Insect repellent NOMENCLATURE: Common name butopyronoxyl (US Pharmacopoeia) IUPAC name butyl 3,4-dihydro-2,2-dimethyl-4-oxo-2H-pyran-6-carboxylate (I) Chemical Abstracts name (I) Other names dihydropyrone; butyl mesityloxide oxalate CAS RN [532–34–3] Smiles code CCCCOC(=O)/C/1=C/C(=O)CC(C)(C)O1; without stereochemistry: CCCCOC(=O)C1=CC(=O)CC(C)(C)O1 PHYSICAL CHEMISTRY: Composition Tech. contains ≥85% butopyronoxyl with ≤2% mesityl oxide; the remainder is mainly dibutyl oxalate and butanol. It exists mainly as the dihydropyrone (I) but with the open chain enol (II) in equilibrium (S.A. Hall et al., J. Am. Chem. Soc., 1945, 67, 1224). Mol. wt. 226.3 M.f. C 12 H 18 O 4 Form Yellow to pale red liquid with a mild aromatic odour. B.p. 90% distils between 256–270 °C S.g./density 1.052–1.060 (20 °C) Solubility Practically insoluble in water and glycerol. Slightly soluble in ethylene glycol, refned petroleum oils; miscible with chloroform, ethanol, diethyl ether, glacial acetic acid. COMMERCIALISATION: History Insect repellent introduced by US Industrial Chemicals Inc. and by Kilgore Chemicals. Patents US 2138540 PRODUCTS: Discontinued products ‘Indalone’* (FMC). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 7840, guinea pigs 3200 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 10 000 mg/kg. Not a skin irritant but may cause a stinging sensation. NOEL In 2 y feeding trials, some growth retardation was observed in rats receiving 80 g/kg diet. Toxicity Class WHO (a.i.) U Details PM6, p. 66. 74 The Pesticide Manual Sixteenth Edition © BCPC 2012 butoxy(polypropylene glycol) 2-(2-butoxyethoxy)ethyl piperonylate Insecticide synergist NOMENCLATURE: IUPAC name 2-(2-butoxyethoxy)ethyl piperonylate Chemical Abstracts name 2-(2-butoxyethoxy)ethyl 1,3-benzodioxole-5-carboxylate Other names BCP CAS RN [136–63–0] Smiles code CCCCOCCOCCOC(=O)c1ccc2OCOc2c1 PHYSICAL CHEMISTRY: Mol. wt. 310.3 M.f. C 16 H 22 O 6 COMMERCIALISATION: History Synergist for pyrethrum introduced by Bush Boake & Allen. APPLICATIONS: Uses A pyrethrum synergist. PRODUCTS: Discontinued products ‘Bucarpolate’* (Bush Boake & Allen). 2-(2-butoxyethoxy)ethyl thiocyanate Insecticide NOMENCLATURE: IUPAC name 2-(2-butoxyethoxy)ethyl thiocyanate (I) Chemical Abstracts name (I) Other names butyl ‘Carbitol’ thiocyanate; butyl ‘Carbitol’ rhodanate; beta-butoxy-beta’-thiocyanodiethyl ether CAS RN [112–56–1] Smiles code CCCCOCCOCCSC#N PHYSICAL CHEMISTRY: Mol. wt. 203.3 M.f. C 9 H 17 NO 2 S COMMERCIALISATION: History Insecticide reported by D. F. Murphy & C. H. Peet (J. Econ. Entomol., 1932, 25, 123). Introduced by Rohm & Haas Co. PRODUCTS: Discontinued products ‘Lethane 384’* (Rohm & Haas). MAMMALIAN TOXICOLOGY: EC Classifcation R10| T; R24/25 butoxy(polypropylene glycol) Insect repellent NOMENCLATURE: Common name butoxy(polypropylene glycol) (ESA) IUPAC name α-hydroxypropyl-o-butoxypoly[oxy(1-methylethylene)] Chemical Abstracts name α-butyl-o-hydroxypoly[oxy(methyl-1,2-ethanediyl)] Supplementary Entries – Extended butroxydim 75 CAS RN [9003–13–8] COMMERCIALISATION: History Fly repellent. Introduced by Union Carbide Corp. PRODUCTS: Discontinued products ‘Crag Fly Repellent’* (Union Carbide). butroxydim Herbicide HRAC A WSSA 1; cyclohexanedione oxime NOMENCLATURE: Common name butroxydime ((m) F-ISO); butroxydim (BSI, E-ISO) IUPAC name 5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3- hydroxycyclohex-2-enone Chemical Abstracts name 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-[2,4,6-trimethyl- 3-(1-oxobutyl)phenyl]-2-cyclohexen-1-one CAS RN [138164–12–2] EC no 414–790–3 Development codes ICIA0500 (ICI) Smiles code CCCC(=O)c1c(C)cc(C)c(C2CC(=C(C(=NOCC)CC)C(=O)C2)O)c1C PHYSICAL CHEMISTRY: Mol. wt. 399.5 M.f. C 24 H 33 NO 4 Form Off-white powdery solid. M.p. 80.8 °C V.p. 1 × 10 –3 mPa (20 °C) K ow logP = 1.90 (pH 7, 25 °C) Henry 5.79 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.20 (tech., 25 °C) Solubility In water 6.9 mg/l (pH 5.5, 20 °C). In dichloromethane >500, acetone 450, toluene 480, acetonitrile 380, methanol 90, hexane 30 (all in g/l). Stability Hydrolysis DT 50 10.5 d (pH 5), >240 d (pH 7), stable (pH 9) (all 25 °C). pKa 4.36 (23 °C), weak acid COMMERCIALISATION: History First sold in 1995. Divested to Crop Care Australasia Pty Ltd in 2002. APPLICATIONS: Biochemistry Fatty acid synthesis inhibitor, by inhibition of acetyl CoA carboxylase (ACCase). Mode of action Post-emergence herbicide. Uses A post-emergence grass herbicide for use on broad-leaved crops, at 25–75 g/ha. Formulation types WG . PRODUCTS: Discontinued products ‘Falcon’* (Crop Care). CH 2 CH 3 N OCH 2 CH 3 OH O CH 3 CH 3 CH 3 CH 3 (CH 2 ) 2 O 76 The Pesticide Manual Sixteenth Edition © BCPC 2012 buturon ANALYSIS: Residues determined by hplc with uv detection, or by hplc-ms. MAMMALIAN TOXICOLOGY: Oral LD 50 for male rats 3476, female rats 1635 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Moderate skin irritant; mild eye irritant (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 (4 h) for rats >2.99 mg/l. NOEL NOAEL (1 y) for dogs 5 mg/kg b.w. daily; NOEL (2 y) for rats 2.5, mice 10 mg/kg b.w. daily (liver tumours only in males at high dose); NOEL developmental for rats 5, rabbits 15 mg/kg b.w. daily. ADI/RfD 0.025 mg/kg. Other Genotoxicity negative. Not oncogenic (rats). Toxicity Class WHO (a.i.) III. EC Classifcation (T; R61| R22| R38| N; R50, R53) ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks >2000, bobwhite quail 1221 mg/kg. Sub-acute dietary LC 50 (5 d) for mallard ducks >5200, bobwhite quail 5200 mg/kg. Fish LC 50 (96 h) for rainbow trout >6.9, bluegill sunfsh 8.8 mg/l. Daphnia LC 50 (48 h) >3.7 mg/l. Algae EbC50 for Selenastrum capricornutum 0.71 mg/l. Bees LD 50 (contact, 24 h) >200 μg/bee. Worms LC 50 (14 d) for Eisenia foetida >1000 mg/kg. ENVIRONMENTAL FATE: Animals In rats, following oral administration, >90% of the dose is excreted within 7 d. Various oxidative transformations of the butyryl chain dominate the metabolic pathway. Neither parent nor metabolites bioaccumulate in tissues. Plants Rapidly metabolised in plants. Soil/Environment Soil K oc 6–1270 (stronger adsorption in low pH soils). Rapid degradation in aerobic soil, lab. DT 50 c. 9 d (20 °C, 40% MHC, pH 7.0, 4.09% o.m.); metabolites include 5-(3-butyryl-2,4,6-trimethylphenyl)-3-hydroxy-2-(1-iminopropyl) cyclohex-2-enone, 6-(3-butyryl-2,4,6-trimethylphenyl)-2-ethyl-4,5,6,7-tetrahydro-4-oxo- 1,3-benzoxazole, 2-(3-butyryl-2,4,6-trimethylphenyl)glutaric acid and 5-(3-butyryl-2,4,6- trimethylphenyl)-3-hydroxy-2-propionylcyclohex-2-enone. Details PM15, Entry 113. buturon Herbicide NOMENCLATURE: Common name buturon (BSI, E-ISO, (m) F-ISO) IUPAC name 3-(4-chlorophenyl)-1-methyl-1-(1-methylprop-2-ynyl)urea Chemical Abstracts name N′-(4-chlorophenyl)-N-methyl-N-(1-methyl-2-propynyl)urea CAS RN [3766–60–7] Development codes H 95 (BASF) Smiles code CC(C#C)N(C) C(=O)Nc1ccc(Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 236.7 M.f. C 12 H 13 ClN 2 O Form Colourless solid. M.p. 145–146 °C; (tech., 132–142 °C) V.p. 0.01 mPa (20 °C) Henry 7.89 × 10 –5 Pa m 3 mol –1 (calc.) Solubility In water 30 mg/l (20 °C). In acetone 279, benzene 9.8, methanol 128 (all in g/kg, 20 °C). Supplementary Entries – Extended sec-butylamine 77 Stability Stable under normal conditions (1<pH<13), but slowly decomposes in boiling water. COMMERCIALISATION: History Herbicide reported by A. Fischer (Meded. Landbouwhogesch. Opzoekingsstn. Staat Gent, 1964, 29, 719). Introduced by BASF AG. Patents DE 1108977 APPLICATIONS: Biochemistry Inhibits photosynthesis. Mode of action Selective, systemic herbicide; uptake is predominantly via the roots. Uses A pre-em. and post-em. herbicide, absorbed mainly by the roots and recommended for use at 0.5–1.5 kg/ha in cereals and maize for the control of shallow-germinating grasses and broad-leaved weeds. Formulation types WP. PRODUCTS: Discontinued products ‘Eptapur’* (BASF); Discontinued mixtures ‘Basftox’* (+ isonoruron) (BASF). ANALYSIS: Product analysis by hydrolysis and potentiometric titration of the 4-chloroaniline produced. Residues determined by hydrolysis and colorimetric estimation of the 4-chloroaniline produced. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3000 mg/kg. Skin and eye Applications (20 h) to the backs of rabbits produced a slight erythema but the ears were unaffected. NOEL In 120 d feeding trials, rats receiving 500 mg/kg diet showed no ill-effect. Other I.p. LD 50 for mice c. 500 mg/kg. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Bees Not toxic to bees. ENVIRONMENTAL FATE: Plants It is rapidly degraded in plants. Soil/Environment In soil, bacterial degradation under the infuence of CO 2 , probably involving 4-chloroaniline formation. Twelve weeks after use, no active substance is biologically detectable. Details PM8, Entry 01650. sec-butylamine Fungicide NOMENCLATURE: Common name (RS)-sec-butylamine (proposed E-ISO, in lieu of a common name) IUPAC name (RS)-sec-butylamine; (RS)-2-aminobutane Chemical Abstracts name 2-butanamine CAS RN [13952–84–6] (RS)-sec-butylamine; CH 3 CH 2 CH(CH 3 )NH 2 78 The Pesticide Manual Sixteenth Edition © BCPC 2012 sec-butylamine [13250–12–9] (R)-sec-butylamine; [513–49–5] (S)-sec-butylamine EC no 237–732–7 (RS)- isomer; 236–232–6 (R)- isomer; 208–164–7 (S)- isomer Smiles code CCC(C)N PHYSICAL CHEMISTRY: Composition Tech. is 99%. Mol. wt. 73.1 M.f. C 4 H 11 N Form Colourless liquid, with an ammoniacal odour. M.p. <–100 °C B.p. 63–65 °C V.p. 18 kPa (20 °C) K ow logP = 0.74 S.g./density 0.724 (20 °C) Solubility Miscible with water and with most organic solvents. With acids, forms water-soluble salts. Stability Stable at room temperature. Exothermic reaction with acids. pKa Base, forming water-soluble salts with acids. F.p. –19.5 °C (DIN 51755) COMMERCIALISATION: History Fungicidal properties of this fumigant reported by J. W. Eckert & M. J. Kolbezen (Nature (London), 1962, 194, 188). Introduced by BASF AG in 1971; registration transferred to Hortichem in 1992 (now Certis UK). APPLICATIONS: Mode of action Fumigant fungicide. Uses Fungicidal fumigation of seed and ware potatoes for control of skin spot and gangrene. As fungicidal dips or sprays on harvested fruit, e.g. control of citrus blue and green moulds and stem rot of oranges. Prevention of Botrytis on chrysanthemums and gladioli during storage and transit. Formulation types SL . PRODUCTS: Discontinued products ‘Butafume’* (BASF); ‘Deccotane’* (post-harvest) (Decco Cerexagri); ‘Tutane’* (DowElanco). ANALYSIS: Product analysis by acid-base titration. Residues determined by glc of a derivative (Anal. Methods Pestic. Plant Growth Regul., 1976, 8, 251; E. W. Day et al., J. Assoc. Off. Anal. Chem., 1968, 51, 39; Resid. Anal. Methods). See also Pestic. Anal. Man., II, 186.450. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 37 (1981). ICSC.401 (1999). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 380, dogs 225 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2500 mg/kg. Irritating to skin and eyes. Inhalation Vapours dangerous if inhaled. NOEL In 2 y feeding trials, teratogenicity studies, reproduction studies, rats and dogs receiving 2500 mg/kg diet suffered no ill-effect. In teratogenicity studies, NOEL: for rats 2500 mg/kg diet; for rabbits 5000 mg/kg diet. In reproduction studies in rats, NOEL 2500 mg/kg diet. ADI/RfD (JMPR) Temporary ADI withdrawn [1984]. Toxicity Class WHO (a.i.) II. EC Classifcation F; R11| Xn; R20/22| C; R35| N; R50 (for (R)-, (S)-, or (RS)- isomers) ECOTOXICOLOGY: Birds Acute oral LD 50 for hens 250 mg/kg. Fish LC 50 for young bluegill sunfsh >50 mg/l. Daphnia EC 50 /LC 50 (48 h) 40.4 mg/l. Algae EC 50 /LC 50 (72 h) 0.54 mg/l. Supplementary Entries – Extended calcium and lead arsenate 79 cadmium calcium copper zinc chromate sulfate Fungicide NOMENCLATURE: IUPAC name cadmium calcium copper zinc chromate sulfate (I) Chemical Abstracts name (I) CAS RN [12001–20–6] Development codes Fungicide 531 COMMERCIALISATION: History Fungicide introduced by Union Carbide Corp. (later Rhône-Poulenc Ag.). PRODUCTS: Discontinued products ‘Crab Turf Fungicide’* (Union Carbide). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 200 (1998) is a general review of copper and copper compounds. calcium and lead arsenate Herbicide, insecticide NOMENCLATURE: Chemical Abstracts name tricalcium arsenate CAS RN [7778–44–1]; [7778–39–4] (arsenic acid) PHYSICAL CHEMISTRY: Mol. wt. 398.1 M.f. As 2 Ca 3 O 8 M.p. 35 °C (arsenic acid) V.p. 0.0 (for acid or salt?) Solubility Insoluble in water and organic solvents. The wettable powder, when made up in aqueous solution, should contain less than 0.5% of dissolved As 2 O 5 , which originates from impurities. Stability Moisture and carbon dioxide cause slow decomposition to calcium carbonate and (phytotoxic) dicalcium hydrogen arsenate. In the presence of acids, water-soluble, strongly phytotoxic arsenic acid is produced. pKa pKa1 2.3, pKa2 7.1 (J. Ag. & Food Chem., 24, 717 (1976)) (for acid). APPLICATIONS: Uses Pre-emergence herbicidal treatment of turf and lawns to control crabgrass. Controls chickweed, annual bluegrass, and certain soil insects, including Japanese beetle. Phytotoxicity Foliage of stone fruit is particularly susceptible. Plant damage can occur in the presence of water-soluble arsenic compounds. Formulation types DP; WP; RB; GR . PRODUCTS: Discontinued products ‘Pencal’* (Pennwalt); ‘Security’* (Woolfolk); ‘Security’* (Woolfolk). ANALYSIS: Product analysis described (AOAC Methods, 18th Ed., 921.05, 921.06, 922.03, 925.03, 963.06); lead arsenate ibid., 920.16–920.21. Residue analysis by mineralisation of the sample, distillation of the arsenic, and determination colorimetrically at 540 nm, as the arsine complex with silver diethyldithiocarbamate (Man. Pestic. Residue Anal., 230). 80 The Pesticide Manual Sixteenth Edition © BCPC 2012 calcium cyanamide TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 224 (2001). JMPR Evaln. 11 (1968), 31 (1978) for lead arsenate. HSG 70 (1992). ICSC.765 (1999) for calcium arsenate; ICSC.911 (1997) for lead arsenate. IARC 87 (2006) (inorganic lead); 23 (1980), Suppl 7 (1987) (arsenic compounds). MAMMALIAN TOXICOLOGY: IARC Class 1 (evaluation applies to arsenic compounds as a whole, not necessarily to all individual compounds within the group); 2A (inorganic lead) Oral Acute oral LD 50 for rats 20 mg/kg; (lead saltc. 10 mg/kg). NOEL 0.42 mg/kg b.w. (EPA Tracking). ADI/RfD (JMPR) No ADI [1968], also for lead salt; (EPA) 0.0042 mg/kg b.w. [1968]. Other Acute oral LD 50 for rats 20, rabbits 50, dogs 38 mg/kg. Dermal resorption is minimal. Toxicity Class WHO (a.i.) Ib (also for lead salt) EC Classifcation R45| T; R23/25| N; R50, R53 (for arsenic acid and salts) ECOTOXICOLOGY: Fish Very toxic to fsh. Bees Toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Inorganically-bound arsenic remains unchanged for a long time in the soil. The alleged microbial reduction to arsine and volatilisation is disputed. calcium cyanamide Fertiliser, fungicide, herbicide NOMENCLATURE: IUPAC name calcium cyanamide Chemical Abstracts name calcium cyanamide CAS RN [156–62–7] EC no 205–861–8 Smiles code [Ca+2].[N-]=C=[N-] PHYSICAL CHEMISTRY: Mol. wt. 80.10 M.f. CCaN 2 M.p. c. 1200 °C (sublimes 1150–1200 °C) S.g./density 2.29 (4–20 °C) Solubility Insoluble in water, but gradually hydrolyses. Insoluble in organic solvents. Stability Very stable under dry storage conditions. Decomposed in moist conditions and in the presence of acids, to calcium hydrogen cyanamide, cyanamide, and urea. COMMERCIALISATION: History Used as a fertiliser since 1905. Later introduced as herbicide and defoliant by American Cyanamid Co., but these uses now discontinued. APPLICATIONS: Mode of action Pre- and post-emergence herbicide and defoliant, with secondary fungicidal action. Produces hydrogen cyanamide upon contact with soil moisture, which is toxic to plants, seeds, and disease organisms. Uses Fertiliser with secondary control of weeds in cereals, maize, vines, feld crops, vegetables, and in meadows and pastures. Also fungicidal control of eyespot in cereals, and club root in brassicas. Cyanamide (q.v. in Main Supplementary Entries – Extended cambendichlor 81 entries) is used as a herbicide and plant growth regulator. Phytotoxicity The chlorophyll of most plants is sensitive, especially in humid conditions. Formulation types GR . PRODUCTS: Discontinued products ‘Cyanamid’* (Cyanamid). ANALYSIS: Product analysis by determination of nitrogen by the Kjeldahl process. Residues in soil by extraction with 0.1 N hydrochloric acid, distillation, clean-up on aluminium oxide and determination of the red complex formed with Na 2 NH 4 [Fe(CN) 5 NH 3 ] spectrophotometrically at 530 nm. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.639 (2006) EU Status (1107/2009) Vote for non-inclusion, SCFCAH 05/2008. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1400 mg/kg. Skin and eye Mild skin irritant. Inhalation LC 50 (4 h) for rats >0.15 mg/l air. Irritation of the mucous membranes of the respiratory tract is evident after inhalation of the dust. Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22| Xi; R37, R41 ECOTOXICOLOGY: Fish Not signifcantly toxic to fsh provided the pH of the water does not exceed 8–8.5. Bees Not toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Taken up into plants and fermentatively degraded. After 9 days, no cyanamide nitrogen is detectable in potatoes. Details PM5, p. 72. cambendichlor Herbicide NOMENCLATURE: Common name cambendichlor (BSI, E-ISO, ANSI, WSSA); cambendichlore ((m) F-ISO) IUPAC name 2,2′-(phenylimino)diethylene bis(3,6-dichloro-o-anisate) Chemical Abstracts name (phenylimino)di-2,1-ethanediyl bis(3,6-dichloro- 2-methoxybenzoate) CAS RN [56141–00–5] Development codes Vel 4207 Smiles code COc1c(Cl)ccc(Cl)c1C(=O)OCCN(CCOC(=O)c2c(Cl)ccc(Cl)c2OC) c3ccccc3 PHYSICAL CHEMISTRY: Mol. wt. 587.3 M.f. C 26 H 23 Cl 4 NO 6 COMMERCIALISATION: History Herbicide introduced by Velsicol Chemical Corp. (later Sandoz AG). 82 The Pesticide Manual Sixteenth Edition © BCPC 2012 camphechlor camphechlor Insecticide NOMENCLATURE: Common name polychlorcamphene (USSR); camphechlor (BSI, E-ISO); camphé(chlore) ((m) F-ISO); toxaphene (Belgium, Canada, USA) IUPAC name a reaction mixture of chlorinated camphenes containing 67–69% chlorine Chemical Abstracts name toxaphene CAS RN [8001–35–2] EC no 232–283–3 Development codes Hercules 3956 PHYSICAL CHEMISTRY: Composition Composition examined by J. E. Casida et al. (J. Agric. Food Chem., 1974, 22, 653; 1975, 23, 991); 26 components account for about 40% of the product. Mol. wt. 431.8 (approx.) M.f. C 10 H 10 Cl 8 (approx.) Form A yellow wax of mild terpene-like odour. M.p. Softens 70–95 °C V.p. 27000–53000 mPa (25 °C) S.g./density 1.65 (25 °C) Solubility In water c. 3 mg/l (room temperature). Readily soluble in organic solvents including petroleum oils. Stability Dehydrochlorinated by heat, by strong sunlight and by certain catalysts such as iron. COMMERCIALISATION: History Insecticide reported by W. LeRoy Parker & J. R. Beacher (Del. Univ. Agric. Exp. Stn. Bull., 1947, No. 264). Introduced by Hercules Inc. Patents US 2565471; US 2657164 APPLICATIONS: Mode of action Non-systemic, contact and ingested insecticide with some acaricidal action. Uses Control of many insects in cereals, cotton, fruit, maize, vegetables and the control of Cassia obtusifolia in soya beans. Has also been used for the control of animal ectoparasites. A heptachlorobornane and a mixture of two octachlorobornanes are more toxic to insects and mice than other components, and are similarly biodegradable. Phytotoxicity Phytotoxic to cucurbits and some varieties of plum and damson. Formulation types EC. Compatibility Not compatible with strongly alkaline pesticides. PRODUCTS: Discontinued products ‘Agronex Hepta’* (Epro); ‘Altox’* (Hercules); ‘Attac’* (BFC); ‘Toxaphene’* (except in countries where used as common name) (Hercules). ANALYSIS: Product analysis by total chlorine (CIPAC Handbook, 1970, 1, 132) or by tlc (AOAC Methods 18th Ed., 972.05). Residues determined by glc with ECD (Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 514), by gel permeation chromatography and glc (AOAC Methods, 14th Ed., 29.037–29.043) or by spectrometry of a derivative (C. L. Dunn, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 2, 523). See also Pestic. Anal. Man., I, 208, 504. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 45 (1984). JMPR Evaln. 21 (1973). HSG 40 (1990). PDS 20 (1975). ICSC.843 (1997). IARC 79 (2001). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEC as amended by 83/131/EEC and by Commission Regulation 850/2004. Supplementary Entries – Extended carbanolate 83 MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 80–90 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 780–1075 mg/kg. NOEL (2 y) for dogs 10 ppm (0.25 mg/kg b.w.) (EPA Tracking). ADI/RfD (JMPR) No ADI [1973]; (EPA) 0.00025 mg/kg b.w. [1986]. Water GV Excluded from GV derivation (U). Toxicity Class WHO (a.i.) II EC Classifcation R40| T; R25| Xn; R21| Xi; R37/38| N; R50, R53 PIC Yes. ECOTOXICOLOGY: Birds Toxic to birds. Fish LC 50 for young rainbow trout 0.2, young pike 0.1 mg/l. Bees Low toxicity to bees. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, camphechlor accumulates temporarily in body fat, but is rapidly eliminated, partly as the unchanged substance and partly as dechlorinated and partially dechlorinated metabolites. Soil/Environment In soil, becomes tightly bound and is highly resistant to leaching. Persistent in soil (DT 50 varies between 70 d and 12 y, depending on soil type and climate). Details PM8, Entry 01920. carbamorph Fungicide NOMENCLATURE: Common name carbamorph (BSI, E-ISO); carbamorphe ((m) F-ISO) IUPAC name morpholinomethyl dimethyldithiocarbamate Chemical Abstracts name 4-morpholinylmethyl dimethylcarbamodithioate CAS RN [31848–11–0] Development codes MC 833 Smiles code CN(C)C(=S)SCN1CCOCC1 PHYSICAL CHEMISTRY: Mol. wt. 220.4 M.f. C 8 H 16 N 2 OS 2 COMMERCIALISATION: History Fungicide introduced by Murphy Chemical Co. (later DowElanco). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O carbanolate Insecticide, ixodicide NOMENCLATURE: Common name carbanolate (BSI, E-ISO, (m) F-ISO, ESA, JMAF) IUPAC name 6-chloro-3,4-xylyl methylcarbamate 84 The Pesticide Manual Sixteenth Edition © BCPC 2012 carbon disulfde Chemical Abstracts name 2-chloro-4,5-dimethylphenyl methylcarbamate CAS RN [671–04–5] Development codes U 12 927 Smiles code CNC(=O)Oc1cc(C)c(C)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 213.7 M.f. C 10 H 12 ClNO 2 COMMERCIALISATION: History Veterinary insecticide and ixodicide introduced by Upjohn Co. (later Nor-Am). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Banol’* (Upjohn). ANALYSIS: Residues by glc of a derivative (AOAC Methods, 18th Ed., 975.40). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O carbasulam Herbicide NOMENCLATURE: Common name carbasulame ((m) F-ISO); carbasulam (BSI, E-ISO) IUPAC name methyl 4-(methoxycarbonylsulfamoyl)carbanilate Chemical Abstracts name methyl [[4-[(methoxycarbonyl)amino]phenyl] sulfonyl]carbamate CAS RN [1773–37–1] Development codes M&B 9555 Smiles code COC(=O)Nc1ccc(cc1)S(=O)(=O)NC(=O)OC PHYSICAL CHEMISTRY: Mol. wt. 288.3 M.f. C 10 H 12 N 2 O 6 S COMMERCIALISATION: History Herbicide evaluated by May & Baker Ltd (later Rhône-Poulenc Agrochimie). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. carbon disulfde Insecticide, nematicide NOMENCLATURE: Common name carbon disulfde (ESA); carbon disulphide (BSI, E-ISO, accepted in lieu of common name); sulfure de carbone (F-ISO) Supplementary Entries – Extended carbon tetrachloride 85 IUPAC name carbon disulfde Chemical Abstracts name carbon disulfde Other names carbon bisulphide CAS RN [75–15–0] EC no 200–843–6 Smiles code S=C=S PHYSICAL CHEMISTRY: Mol. wt. 76.13 M.f. CS 2 Form Colourless mobile liquid. Its impurities have an unpleasant odour. M.p. –108.6 °C B.p. 46.3 °C V.p. 4.7 × 107 mPa (25 °C) K ow logP = 1.84 (Agchem. Desk Ref.) S.g./density 1.2628 (20 °C); gas, 2.63 (air = 1) Solubility In water 2.2 g/l (32 °C). Miscible with chloroform, diethyl ether, ethanol. F.p.c. 20 °C; ignites spontaneously >100 °C COMMERCIALISATION: History Used as insecticide in 1854 by Garreau (see Science, 1926, 64, 326). APPLICATIONS: Mode of action Fumigant insecticide and nematicide. Uses For fumigation of nursery stock and for soil treatment against insects and nematodes. It was also used in some countries as an insecticide in mixtures with carbon tetrachloride (to reduce fre hazard) for fumigating stored grain. PRODUCTS: Discontinued products ‘Weevil Tox’* (Stauffer). ANALYSIS: Product analysis by glc (AOAC Methods, 18th Ed., 966.05). Residues in grain may be determined by glc (S. G. Heuser & K. A. Scudmore, J. Sci. Food Agric., 1969, 20, 566) or by colorimetry of a derivative (C. L. Dunning, J. Assoc. Off. Agric. Chem., 1957, 40, 168). See also Pestic. Anal. Man., II, 180.467. The concentration in air may be measured by drawing the air through an ethanolic solution of diethylamine and copper(II) acetate and colorimetry of the complex produced. Methods reviewed by J. L. Daft in Comp. Anal. Profles,Chapter 11. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 10 (1979). JMPR Evaln. I 45 (1985); JMPR Evaln. 17 (1971). ICSC.022 (2000). CICAD 46 (2002). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Inhalation The vapour is highly poisonous, producing giddiness and vomiting in 30 min at 6.8 mg/l air; repeated daily exposures to 0.227 mg/l air caused ill health. NOEL Inhalation NOEL for rats 20 ppm (11 mg/kg b.w.) (EPA Tracking). ADI/RfD (JMPR) No ADI [1965]; (EPA) RfD 0.1 mg/kg b.w. [1985]. Toxicity Class WHO (a.i.) FM EC Classifcation F; R11| R62, R63| T; R48/23| Xi; R36/38 (concentration-dependent) Details PM8, Entry 02030. carbon tetrachloride Insecticide NOMENCLATURE: Common name carbon tetrachloride (BSI, E-ISO, ESA, traditional name); té(trachlorure de carbone) (F-ISO, accepted in lieu of a common name) 86 The Pesticide Manual Sixteenth Edition © BCPC 2012 carbon tetrachloride IUPAC name carbon tetrachloride; tetrachloromethane Chemical Abstracts name tetrachloromethane CAS RN [56–23–5] EC no 200–262–8 Smiles code ClC(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 153.8 M.f. CC l4 Form Colourless liquid. M.p. –23 °C B.p. 76 °C V.p. 15 kPa (25 °C) Henry 8.24 × 103 Pa m 3 mol –1 (calc.) S.g./ density 1.588 (25 °C); gaseous, 5.32 (air = 1) Solubility In water 280 mg/kg (25 °C). Miscible with most organic solvents. Stability Though generally inert, it is decomposed by water at high temperatures. F.p. Non-fammable and non-explosive COMMERCIALISATION: History Use as insecticidal fumigant described by W. E. Britton (Conn. Agric. Exp. Stn. Rep., 1908, No. 31). APPLICATIONS: Mode of action Fumigant insecticide Uses Shows weak insecticidal activity, but was used for grain disinfestation when long exposures are possible, its main advantages being low absorption by treated grain. It was often used in mixtures with more potent fumigants, such as ethylene dichloride, to reduce the fre hazard of the latter. It has also been used as an anthelmintic in veterinary practice. ANALYSIS: Product analysis by glc (AOAC Methods, 14th Ed., 6.159–6.164). Residues in stored cereals determined by glc with ECD (ibid., 18th Ed., 977.18; K. A. Scudamore, Anal. Methods Pestic. Plant Growth Regul., 1988, 16, 207, 222; Anal. Methods Residues Pestic., 1988, Part I, M8; Analyst (London), 1974, 99, 570). Methods reviewed by J L Daft in Comp. Anal. Profles,Chapter 11. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 208 (1999). JMPR Evaln. I 45 (1985); JMPR Evaln. 33 (1979). HSG 108 (1998). ICSC.024 (2000). IARC 20 (1979); 71 (1999). MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 5730–9770, mice 12 800, rabbits 6380–9975 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 5070 mg/kg (ESA, Special Publication,1978). NOEL NOAEL for rats 0.71 mg/kg b.w. daily (EPA IRIS). ADI/RfD (JMPR) No ADI [1965]; (EPA) cRfD 0.0007 mg/kg b.w. [1991]. Other It is a general anaesthetic, prolonged exposure causing irritation of the mucous membranes, headache and nausea; repeated exposure to high concentrations causes liver damage. EC Classifcation R40| T; R23/24/25, R48/23| R52, R53| N; R59| concn. dep. Details PM9, Entry 2040. Supplementary Entries – Extended carbophenothion 87 carbophenothion Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name carbophenothion (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name S-4-chlorophenylthiomethyl O,O-diethyl phosphorodithioate Chemical Abstracts name S-[[(4-chlorophenyl)thio]methyl] O,O- diethyl phosphorodithioate CAS RN [786–19–6] EC no 212–324–1 Development codes R-1303 (Stauffer) Smiles code CCOP(=S)(OCC)SCSc1ccc(Cl)cc1 PHYSICAL CHEMISTRY: Composition Tech. is 95%. Mol. wt. 342.9 M.f. C 11 H 16 ClO 2 PS 3 Form Colourless liquid with a mercaptan-like odour; (tech. is a pale amber liquid). B.p. 82 °C /0.01 mmHg V.p. 1.07 mPa (25 °C) K ow logP = 4.75 (Agchem. Desk Ref.) S.g./density 1.271 (25 °C); 1.285 (20 °C, tech.) Solubility In water <1 mg/l (room temperature). Miscible with most organic solvents, e.g. alcohols, esters, ketones, xylene, mineral oils. Miscible with vegetable oils. Stability Thermally stable up to 80 °C. Relatively stable to hydrolysis, particularly in alkaline media. COMMERCIALISATION: History Insecticide and acaricide (Agric. Chem., 1956, 11(11), 91). Introduced by Stauffer Chemical Co. (later ICI Americas). Patents US 2793224 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide and acaricide with contact and stomach action. Long residual activity. Uses Control of aphids and spider mites on citrus fruit and cotton; and spider mites, aphids, suckers, Lepidoptera, and other insect pests in fruit, nut crops, vines, olives, fgs, vegetables, beet, maize, sorghum, clover, alfalfa, cucurbits, soya beans, ornamentals, turf, and other crops. Used as a seed treatment for control of wheat bulb fies in wheat. Used in combination with petroleum oil for control of overwintering aphids, scale insects, and mites on dormant deciduous fruit trees. Also used as an animal ectoparasiticide. Phytotoxicity Slightly phytotoxic. Leaf damage may occur on susceptible apples (Delicious), and on roses under glass, especially under warm, moist conditions. Grapefruits, kumquats, citrons, and some varieties of grape may also suffer injury. Formulation types EC; WP; GR; DP; Seed treatment. PRODUCTS: Discontinued products ‘Trithion’* (Stauffer). Cl S CH 2 S P S OCH 2 CH 3 OCH 2 CH 3 88 The Pesticide Manual Sixteenth Edition © BCPC 2012 carboxazole ANALYSIS: Product by glc with FID (Anal. Methods Pestic. Plant Growth Regul. 1972, 6, 519–521). Residues by glc with TID or FPD (AOAC Methods, 18th Ed., 974.22, 968.24; J. A. Burke J. Assoc. Off. Anal. Chem. 1965, 48, 1037–1058; Anal. Methods Pestic. Plant Growth Regul. 1972, 6, 521–528; D. C. Abbott et al., Pestic. Sci., 1970, 1, 10). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. JMPR Evaln. 41 (1983). ICSC.410 (1997). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 79.4, female rats 20, mice 218 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 1850, male rats 54, female rats 27 mg/ kg. NOEL LOEL (2 y) for dogs 5 ppm (0.125 mg/kg b.w.) (EPA Tracking). ADI/RfD (JMPR) 0.0005 mg/kg b.w. [1980]; (EPA) 0.00013 mg/kg b.w. [1987]. Toxicity Class WHO (a.i.) Ib EPA (formulation) I EC Classifcation T; R24/25| N; R50, R53 ECOTOXICOLOGY: Fish Very toxic to fsh. Bees Moderately toxic to bees. ENVIRONMENTAL FATE: Animals Readily degraded in rats, primarily to water soluble products which are excreted in the urine (FAO/WHO 28). Plants On leaf surfaces, oxidation occurs to the phosphorothioate (B. J. Luberoff et al., Agric. Chem., 1958, 13(3), 83). Soil/Environment Undergoes oxidation to the sulfone, sulfoxide, thiol, thiosulfone, and thiosulfoxide, presumably combined with dealkylation and hydrolysis. Details PM8, Entry 02050. carboxazole Herbicide NOMENCLATURE: Common name carboxazole (BSI, E-ISO, (m) F-ISO) IUPAC name methyl 5-tert-butyl-1,2-oxazol-3-ylcarbamate; methyl 5-tert-butylisoxazol- 3-ylcarbamate Chemical Abstracts name methyl [5-(1,1-dimethylethyl)-3-isoxazolyl]carbamate CAS RN [55808–13–4] Development codes SSH-42 Smiles code COC(=O)Nc1cc(on1)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 198.2 M.f. C 9 H 14 N 2 O 3 COMMERCIALISATION: History Herbicide evaluated by Shionogi & Co. Ltd. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. Supplementary Entries – Extended CGA 80 000 89 CECA Fungicide NOMENCLATURE: Common name CECA (JMAF) IUPAC name 2-chloro-N-(2-cyanoethyl)acetamide (I) Chemical Abstracts name (I) CAS RN [17756–81–9] Development codes NF 21 Smiles code ClCC(=O)NCCC#N PHYSICAL CHEMISTRY: Mol. wt. 146.6 M.f. C 5 H 7 ClN 2 O COMMERCIALISATION: History Fungicide introduced by Nippon Soda Co., Ltd. PRODUCTS: Discontinued products ‘Udonkor’* (Nippon Soda). CGA 80 000 Fungicide NOMENCLATURE: IUPAC name (RS)-α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone Chemical Abstracts name (±)-N-(3-chloro-2,6-dimethylphenyl)-2-methoxy-N- (tetrahydr-2-oxo-3-furanyl)acetamide CAS RN [79555–80–9] racemate; [67932–85–8] unstated stereochemistry Development codes CGA 80 000 Smiles code COCC(=O)N(C1CCOC1=O)c2c(C)ccc(Cl)c2C PHYSICAL CHEMISTRY: Mol. wt. 311.8 M.f. C 15 H 18 ClNO 4 M.p. 94.9 °C V.p. 5 × 10 –4 mPa (20 °C) K ow logP = 1.5 (unspecifed organic phase, reversed-phase tlc) Henry 2.29 × 10 –7 Pa m 3 mol –1 (calc.) Solubility In water 680 mg/l (20 °C). Stability Stable to hydrolysis at pH 1 to 5; DT 50 154 d (pH 7), 19 d (pH 8) (20 °C). COMMERCIALISATION: History Fungicide reported by P. Margot et al. (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., 2, 527). Evaluated by Ciba-Geigy AG. APPLICATIONS: Mode of action Systemic fungicide. Uses Control of soil-borne late blight and root rot on tobacco, citrus, avocado, carrots, soft fruit, and ornamentals. Formulation types GR; SC. PRODUCTS: Discontinued products ‘Vangard’* (Cyanamid). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 808 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Not a skin or eye irritant. Marginal skin sensitiser (guinea-pigs). Inhalation LC 50 (4 h) >1.7 mg/l air. 90 The Pesticide Manual Sixteenth Edition © BCPC 2012 chinomethionat ECOTOXICOLOGY: Fish Non-toxic. Bees Non-toxic. chinomethionat Acaricide, fungicide IRAC UN NOMENCLATURE: Common name chinomethionat (E-ISO); no name (USA); quinoxalines (JMAF); chinomé(thionate) ((m) F-ISO); quinomethionate (BSI); oxythioquinox (Australia, ESA) IUPAC name S,S-(6-methylquinoxaline-2,3-diyl) dithiocarbonate; 6-methyl-1,3- dithiolo[4,5-b]quinoxalin-2-one Chemical Abstracts name 6-methyl-1,3-dithiolo[4,5-b]quinoxalin-2-one CAS RN [2439–01–2] EC no 219–455–3 Development codes Bayer 36 205; Bayer SAS 2074 Offcial codes ENT 25 606 Smiles code Cc1ccc2nc3sc(=O)sc3nc2c1 PHYSICAL CHEMISTRY: Mol. wt. 234.3 M.f. C 10 H 6 N 2 OS 2 Form Yellow crystals. M.p. 170 °C V.p. 0.026 mPa (20 °C) K ow logP = 3.78 (20 °C) Henry 6.09 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.556 (20 °C) Solubility In water 1 mg/l (20 °C). In toluene 25, dichloromethane 40, hexane 1.8, isopropanol 0.9, cyclohexanone 18, DMF 10, petroleum oils 4 (all in g/l, 20 °C). Soluble in hot benzene and dioxane. Stability Relatively stable under normal conditions. Hydrolysed in alkaline media; DT 50 (22 °C) 10 d (pH 4), 80 h (pH 7), 225 min (pH 9). COMMERCIALISATION: History Acaricide and fungicide reported by K. Sasse (Hoefchen-Briefe (Engl. Ed.), 1960, 13, 197; K. Sasse et al., Angew. Chem., 1960, 72, 973). Introduced by Bayer AG. Patents DE 1100372; BE 580478 APPLICATIONS: Mode of action Selective non-systemic contact fungicide with protective and eradicant action. Uses Control of powdery mildews and spider mites on fruit (including citrus), ornamentals, cucurbits, cotton, coffee, tea, tobacco, walnuts, vegetables, and glasshouse crops; and American gooseberry mildew on gooseberries and currants. Phytotoxicity Phytotoxic to certain varieties of apple, pear, currant, rose, and ornamentals. Formulation types DP; FU; SC. WP. Compatibility Incompatible with mineral oils (phytotoxicity may result), and with formulations based on thiram. N N S S O CH 3 Supplementary Entries – Extended chinomethionat 91 PRODUCTS: Discontinued products ‘Morestan’* (Bayer CropScience); Discontinued mixtures ‘Morestan VP’* (+ dichlorvos) (Nippon Soda). ANALYSIS: Product analysis by hplc (CIPAC Handbook, 1985, 1C, 2019; AOAC Methods, 18th Ed., 986.08) or by uv spectrometry (details available from Bayer CropScience). Residues determined by glc (Man. Pestic. Residue Anal., p. 13; A. Ambrus et al., J. Assoc. Off. Anal. Chem., 1981, 64, 733; R. T. Krause & E. M. August, ibid., 1983, 66, 1018), or by colorimetry after conversion to a derivative (H. Tietz et al., ibid., 1962, 15, 166; C. A. Anderson, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1967, 5, 277). See also Pestic. Anal. Man., I, 302; ibid., II 180.338. Methods for the determination of residues are also available from Bayer CropScience. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 43 (1984); JMPR Evaln. II 52 (1987). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 2541, female rats 1095 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Slightly irritating to skin; severely irritating to eyes (rabbits). Inhalation LC 50 (4 h) for male rats >4.7, female rats 2.2 mg/l (dust). NOEL (2 y) for rats 40, male mice 270, female mice <90 mg/kg diet; (1 y) for dogs 25 mg/ kg diet (0.625 mg/kg b.w.). ADI/RfD (JMPR) 0.006 mg/kg b.w. [1987]; (EPA) 0.006 mg/kg b.w. [1999]. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation R62| Xn; R20/21/22, R48/22| Xi; R36| R43| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 196 mg/kg. Dietary LC 50 (5 d) for bobwhite quail 2409, mallard ducks >5000 mg/kg diet. Fish LC 50 (96 h) for bluegill sunfsh 0.0334, rainbow trout 0.131, golden orfe 0.24 mg/l. Daphnia LC 50 (48 h) 0.12 mg/l. Algae ErC50 (96 h) for Scenedesmus 0.14 mg/l. Bees Not toxic to bees; LD 50 >100 μg/bee. Worms LC 50 (14 d) >1000 mg/kg. ENVIRONMENTAL FATE: Animals In rats, following oral administration, chinomethionat is rapidly metabolised, andc. 90% is eliminated within 3 days in the faeces and urine. The main metabolite is chinomethionat acid (dimethylmercaptoquinoxaline-6-carboxylic acid), which also occurs in the conjugated form. Plants After application to fruit, no penetration of the a.i. or metabolites in the fruit pulp was observed. The only metabolite detected was dihydromethylquinoxalinedithiol. Soil/Environment K oc 45–90 (3 soil types from sandy loam to high organic matter). DT 50 in standard soil land 2 1–3 d. Details PM15, Entry 134. 92 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlomethoxyfen chlobenthiazone Fungicide NOMENCLATURE: Common name chlobenthiazone (BSI, E-ISO, (f) F-ISO) IUPAC name 4-chloro-3-methyl-1,3-benzothiazol-2(3H)-one; 4-chloro-3- methylbenzothiazol-2(3H)-one Chemical Abstracts name 4-chloro-3-methyl- 2(3H)-benzothiazolone CAS RN [63755–05–5] Development codes S-1901 Smiles code Cn1c(=O)sc2cccc(Cl)c12 PHYSICAL CHEMISTRY: Mol. wt. 199.7 M.f. C 8 H 6 ClNOS Form Colourless crystals. M.p. 131–132 °C V.p. 172 mPa (20 °C) Henryc. 7.47 × 10 –1 Pa m 3 mol –1 (calc.) Solubility In water 46 mg/ kg (21.5 °C). In acetone, methanol, xylene 330, chloroform, cyclohexanone 500, ethyl acetate 200 (all in g/kg, 21.5 °C). Stability Stable in aqueous acid and alkali. COMMERCIALISATION: History Fungicide reported by S. Inoue et al. (Proc. 1981 Br. Crop. Prot. Conf. - Pests Dis., 1981, 1, 19). Evaluated by Sumitomo Chemical Co., Ltd. APPLICATIONS: Mode of action Systemic fungicide. It inhibits the development of infection pegs from appressoria. Uses Submerged applications of granules (2.4–3.2 kg/ha) or foliar applications of a dust are effective in controlling Pyricularia oryzae in rice. Formulation types DP; GR . MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 1940, female rats 2170, male mice 1430, female mice 1250 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and mice >2500 mg/kg. Not irritant to the abraded skin of rabbits; minimally irritant to their eyes. NOEL In 0.5 y feeding trials, rats receiving 100 mg/kg diet showed no ill-effect. chlomethoxyfen Herbicide HRAC E WSSA 14; diphenyl ether S N O CH 3 Cl Cl OCH 3 O NO 2 Cl Supplementary Entries – Extended chlomethoxyfen 93 NOMENCLATURE: Common name chlomé(thoxyfè) ((m) F-ISO); chlormethoxynil (JMAF); chlomethoxyfen (BSI, E-ISO) IUPAC name 5-(2,4-dichlorophenoxy)-2-nitroanisole Chemical Abstracts name 4-(2,4-dichlorophenoxy)-2-methoxy-1-nitrobenzene; 2,4-dichloro-1-(3-methoxy-4-nitrophenoxy)benzene CAS RN [32861–85–1] Development codes X-52 Smiles code COc1cc(Oc2ccc(Cl)cc2Cl)ccc1[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 314.1 M.f. C 13 H 9 Cl 2 NO 4 Form Yellow crystals. M.p. 113–114 °C B.p. 260 °C /25 mmHg V.p. 1.87 mPa (25 °C) K ow logP = 3.34 (20 °C) S.g./density 1.37 Solubility In water 0.3 mg/l (15 °C). In acetone 200, DMSO 100, benzene 150 (all in g/kg, 15 °C). Stability Stable to acids, alkalis, and light. COMMERCIALISATION: History Introduced as a herbicide by Nihon Nohyaku Co., Ltd. Patents JP 600441 Manufacturers Ishihara Sangyo APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. Mode of action Selective contact herbicide, absorbed by the leaves and stems. Uses Pre-emergence control of Scirpus spp., Echinochloa crus-galli, and other annual weeds in transplanted rice at 1.5–2.5 kg/ha. Phytotoxicity May scorch old leaves. Formulation types WP; GR . PRODUCTS: Discontinued products ‘Condore’* (Ishihara Sangyo); ‘Difenex’* (Ishihara Sangyo); ‘Diphenex’* (Ishihara Sangyo); ‘Ekkusugoni’* (Ishihara Sangyo, Nihon Nohyaku); ‘Ikkokuso’* (Ishihara Sangyo). ANALYSIS: Product analysis by glc with FID (F. Yamane & K. Tsuchiya, Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 267). Residues determined by glc with ECD (idem, ibid.). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Inhalation LC 50 for rats >1.767 mg/l. Toxicity Class WHO (a.i.) U EPA (formulation) IV ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 11.2 mg/l. Daphnia LC 50 (24 h) >47.5 mg/l. ENVIRONMENTAL FATE: Animals Metabolised in rats to form glucurone and glutathione conjugates. Soil/Environment In soil, DT 50 7–43 d. K d 525–1407. Details PM11, Entry 117. 94 The Pesticide Manual Sixteenth Edition © BCPC 2012 chloramben chloramben Herbicide HRAC O WSSA 4; benzoic acid (auxin) NOMENCLATURE: Common name chloramben (BSI, E-ISO, ANSI, WSSA); amben* (former WSSA name); chlorambè(n) ((m) F-ISO) IUPAC name 3-amino-2,5-dichlorobenzoic acid Chemical Abstracts name 3-amino-2,5-dichlorobenzoic acid CAS RN [133–90–4] Development codes ACP M-629 (Amchem) Smiles code Nc1cc(Cl)cc(C(=O)O)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 206.0 M.f. C 7 H 5 Cl 2 NO 2 Form Colourless crystals. M.p. 200–201 °C V.p. 930 mPa (100 °C) Solubility In water 700 mg/l (25 °C). In DMF 1206, acetone, methanol 223, ethanol 173, isopropanol 113, diethyl ether 70, chloroform 0.9, benzene 0.2 (all in g/kg, room temperature). Insoluble in carbon tetrachloride. Stability Thermally stable up to the boiling point. Stable to oxidising agents, acids and alkalis. Decomposed by sodium hypochlorite solutions. Sensitive to light. pKa 3.40 (ACS Adv. in Chem. Series no. 111, cited in ARS PPD). COMMERCIALISATION: History Herbicide introduced by Amchem Products, Inc. (later Bayer AG). Patents US 3014063; US 3174842 APPLICATIONS: Biochemistry Synthetic auxin (acting like indolylacetic acid). The N-glycoside was isolated from soya beans in amounts equivalent to the chloramben applied, but little was recovered from barley, a susceptible crop (S. R. Colby, Science, 1965, 150, 619). Mode of action Selective systemic herbicide, absorbed by the seeds and roots, with limited translocation. Inhibits root development of seedling weeds. Uses Used pre-planting incorporated and pre-emergence, at 2–4 kg/ha, to control grasses and broad-leaved weeds in seedling asparagus, navy beans, peanuts, maize, sweet potatoes, pumpkins, soya beans, squash, sunfowers and certain ornamentals. Formulation types DS; GR; SL; SP. PRODUCTS: Discontinued products ‘Amiben’* (ammonium salt) (Aventis). ANALYSIS: Product analysis by uv spectrophotometry (AOAC Methods, 18th Ed., 971.06; CIPAC Handbook, 1983, 1B, 1747) or volumetric methods. See also: H. S. Segal & M. L. Cl CO 2 H Cl NH 2 Supplementary Entries – Extended chloraniformethan 95 Sutherland, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1967, 5, 321; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 588. Residue analysis by glc of methyl ester. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3160 mg/kg. Mild skin and eye irritant (rabbits). NOEL (2 y) for rats 10 000 mg/kg diet. ADI/RfD (EPA) cRfD 0.015 mg/kg b.w. [1988]. Toxicity Class WHO (a.i.) U EPA (formulation) IV ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks 4640 mg/kg. Fish Not toxic to fsh. Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In rats, the major metabolites were 3-amino-5-chlorobenzoic acid, 3-aminobenzoic acid, 2,5-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid and 2,5-dichloroaniline. Plants In plants, chloramben is converted to a highly stable N-glucoside, which retards further degradation. Soil/Environment Undergoes microbial degradation in soil. Duration of activity isc. 6–8 w. Details PM12, Entry 126. chloraniformethan Fungicide NOMENCLATURE: Common name chloraniformethan (BSI, E-ISO); chloraniformé(thane) ((m) F-ISO) IUPAC name N-[2,2,2-trichloro-1-(3,4-dichloroanilino)ethyl]formamide Chemical Abstracts name N-[2,2,2-trichloro-1-[(3,4-dichlorophenyl)amino] ethyl]formamide CAS RN [20856–57–9] Development codes Bayer 79 770 Smiles code Clc1ccc(NC(NC=O)C(Cl)(Cl)Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 336.4 M.f. C 9 H 7 Cl 5 N 2 O M.p. 134–136 °C V.p. <1 mPa (20 °C);c. 1.3 mPa (40 °C) Henry <2 × 10 –3 Pa m 3 mol –1 (20 °C, calc.) Solubility In water 0.016 g/100 ml (20 °C). In methanol 40, methyl isobutyl ketone 40.2, cyclohexanone 45, DMF 55, toluene 1.33, n-heptane 0.008 (all in g/100 g, 20 °C). Stability Converted by strong acids and alkalis to 3,4-dichloroaniline. COMMERCIALISATION: History Fungicide reported by A. O. Paulus et al. (Calif. Agric., 1968, 22(3), 10). Introduced by Bayer AG. APPLICATIONS: Mode of action Fungicide with curative action. Uses Control of mildew, especially Erysiphe species, in cereals and ornamentals (roses, chrysanthemums, begonias). 96 The Pesticide Manual Sixteenth Edition © BCPC 2012 chloranil PRODUCTS: Discontinued products ‘Imugan’* (Bayer); ‘Milfaron’* (Bayer). ANALYSIS: Product by gc determination, as for residues (R. A. Hoodless & M. Sargent Analyst 1976, 101, 161–166). residues by extraction of plant material by maceration with acetone, clean-up, hydrolysis with sulfuric acid, steam distillation of the resultant 3, 4-dichloroaniline from alkaline solution, diazotization, coupling with N-(1-naphthyl)ethylenediamine, and colorimetric determination at 530 nm (K. Vogeler Pfanz.-Nachr. Bayer 1969, 22, 299–304 and Man. Pestic. Residue Anal., 271). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats >2500, female mice >1000, cats >500, guinea pigs 250–500 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >500 mg/kg. 14 d activity on the skin of rabbits has no detrimental effects on general condition, organs, etc. NOEL Feeding of 10, 30, and 100 mg/kg b.w. for 14 w does not cause any symptoms of toxicity; intake of 100 mg/kg produces liver hypertrophy. Toxicity Class WHO (a.i.) O ECOTOXICOLOGY: Fish LC 50 for goldfsh 1–10 mg/l. Details PM4, p. 91. chloranil Fungicide NOMENCLATURE: Common name chloranil (BSI, E-ISO); chloranile (F-ISO); traditional names accepted in lieu of a common name IUPAC name tetrachloro-p-benzoquinone; 2,3,5,6-tetrachloro-1,4-benzoquinone Chemical Abstracts name 2,3,5,6-tetrachloro-2,5-cyclohexadiene-1,4-dione CAS RN [118–75–2] EC no 204–274–4 Smiles code ClC1=C(Cl)C(=O)C(=C(Cl) C1=O)Cl PHYSICAL CHEMISTRY: Mol. wt. 245.9 M.f. C 6 Cl 4 O 2 M.p. 292 °C (in closed tube) V.p. 1300 mPa (70.7 °C) S.g./density 1.97 Solubility Practically insoluble in water. In acetone 33, ether 16, DMF 5.4, solvent naphtha 5.4, benzene 1.3, methanolc. 0.1, carbon tetrachloridec. 0.1, dibutyl phthalatec. 0.1 (all in g/100 g). Stability Stable in closed containers. Slowly decomposed by sunlight. Decomposed by alkalis; stable in acidic media. COMMERCIALISATION: History Fungicidal activity of chloranil, long known as a chemical reagent, reported by H. S. Cunningham & E. G. Shavelle (Phytopathology, 1940, 30, 4). Introduced by Uniroyal Chemical Co., Inc. Supplementary Entries – Extended chloranocryl 97 APPLICATIONS: Mode of action Fungicide and seed protectant with secondary insect repellent and bactericidal effects. Uses Used particularly on vegetable and ornamental seeds. Active against damping-off on beans. Formulation types WP; DP; DS . PRODUCTS: Discontinued products ‘Spergon’* (Uniroyal). ANALYSIS: Product by reduction of chloranil with potassium iodide and potentiometric titration of the liberated iodine with sodium thiosulfate (Anal. Methods Pestic. Plant Growth Regul., 3, 29), or total chlorine determination by the Stepanov method or Parr bomb decomposition. Residues by extraction with benzene, clean-up, reaction with diphenyl-p-phenylenediamine to give a blue colour, transfer of the dye into the aqueous-acid phase, and determination by spectrophotometry at 700 nm (Anal. Methods Pestic. Plant Growth Regul., 3, 32). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for ratc. 4 g/kg. Skin and eye Slight absorption through the skin; nevertheless there is local irritation. NOEL Long-term feeding as 0.5% of diet causes no damage to health. Other I.p. LD 50 c. 0.5 g/kg. Toxicity Class WHO (a.i.) O EC Classifcation Xi; R36/38| N; R50, R53 ECOTOXICOLOGY: Bees Not toxic to bees. ENVIRONMENTAL FATE: Soil/Environment In plants, the chlorine atoms are replaced by sulfhydryl groups. In solution, under the infuence of sunlight, reduction to tetrachlorohydroquinone followed by replacement of chlorine atoms with hydroxy groups. Details PM5, p. 90. chloranocryl Herbicide NOMENCLATURE: Common name chloranocryl (BSI, E-ISO, (m) F-ISO); dicryl (Canada, WSSA, ex ANSI) IUPAC name 3′,4′-dichloro-2-methylacrylanilide Chemical Abstracts name N-(3,4-dichlorophenyl)-2-methyl-2-propenamide CAS RN [2164–09–2] Development codes FMC 4556 Smiles code CC(=C)C(=O)Nc1ccc(Cl)c(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 230.1 M.f. C 10 H 9 Cl 2 NO COMMERCIALISATION: History Herbicide reported by S. W. Bingham & W. K. Porter (Weeds, 1961, 9, 282). Introduced by FMC Corp. 98 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorazine APPLICATIONS: Mode of action Contact herbicide. PRODUCTS: Discontinued products ‘Dicryl’* (FMC). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Details PM2, p. 85. chlorazifop; chlorazifop-propargyl Herbicide NOMENCLATURE: Common name chlorazifop (BSI, E-ISO, (m) F-ISO) IUPAC name (±)-2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionic acid Chemical Abstracts name (±)-2-[4-[(3,5-dichloro-2-pyridinyl)oxy]phenoxy] propanoic acid CAS RN [60074–25–1] chlorazifop, unstated stereochemistry; [74310–70–6] chlorazifop, racemate; [72492–54–7] chlorazifop, (R)- isomer; [72492–55–8] chlorazifop, (S)- isomer; [72280–52–5] chlorazifop-propargyl, unstated stereochemistry, formerly [77107–49–4]; [74267–69–9] chlorazifop- propargyl, (R)- isomer Development codes CGA 82 725 (chlorazifop-propargyl) Smiles code chlorazifop:CC(Oc1ccc(Oc2ncc(Cl)cc2Cl)cc1)C(=O)O PHYSICAL CHEMISTRY: Mol. wt. 328.2; (propargyl ester 366.2) M.f. C 14 H 11 Cl 2 NO 4 ; (propargyl ester C 17 H 13 Cl 2 NO 4 ) COMMERCIALISATION: History Chlorazifop-propargyl evaluated as a herbicide by Ciba-Geigy AG (chlorazifop also formed by hydrolysis of isoxapyrifop in vivo). chlorazine Herbicide NOMENCLATURE: Common name chlorazine (BSI, WSSA, ex ANSI) IUPAC name 6-chloro-N 2 ,N 2 ,N 4 ,N 4 -tetraethyl-1,3,5-triazine-2,4-diamine Chemical Abstracts name 6-chloro-N,N,N′,N′-tetraethyl-1,3,5-triazine-2,4-diamine CAS RN [580–48–3] Development codes G 25 804 Smiles code CCN(CC)c1nc(Cl)nc(n1)N(CC)CC PHYSICAL CHEMISTRY: Mol. wt. 257.8 M.f. C 11 H 20 ClN 5 COMMERCIALISATION: History Herbicide introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). Supplementary Entries – Extended chlorbenside 99 chlorbenside Acaricide NOMENCLATURE: Common name chlorbenside (BSI, E-ISO, F-ISO, ESA, ex ANSI) IUPAC name 4-chlorobenzyl 4-chlorophenyl sulfde Chemical Abstracts name 1-chloro-4-[[(4-chlorophenyl)methyl]thio] benzene CAS RN [103–17–3] Development codes HRS 860; RD 2195 Smiles code Clc1ccc(CSc2ccc(Cl)cc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 269.2 M.f. C 13 H 10 Cl 2 S M.p. 72.5 °C B.p. 83–84 °C /0.003 mbar V.p. 1.6 mPa (30 °C) Solubility In water <1:5000. In alcohol 2.8%; readily soluble in acetone and benzene. Stability Extremely stable to acids and alkalis. Oxidising agents convert it to the sulfoxide and sulfone. COMMERCIALISATION: History Acaricide reported by J. E. Cranham et al. (Chem. Ind. (London), 1953, p. 1206) and by D. J. Higgons & D. W. Kilbey (ibid., p. 1359). Introduced by The Boots Co., Ltd (later Schering Agrochemicals). APPLICATIONS: Mode of action Specifc acaricide, with ovicidal and larvicidal properties. Little insecticidal activity. Uses Control of most varieties of spider mites (weak activity against adults), particularly in the pre-blossom stage in fruit cultivation and on ornamentals and nursery stock. Phytotoxicity Cucumbers and other cucurbits are susceptible. Formulation types WP; EC. PRODUCTS: Discontinued products ‘Chlorparacide’* (Boots); ‘Chlorsulphacide’* (Boots); ‘Redon’* (Sariaf). ANALYSIS: Product by extraction with ether, hydrolysis to p-chlorophenol, steam distillation, colorimetric determination at 510 nm after colour reaction with 4-aminoantipyrine in the presence of potassium ferricyanide (Anal. Insectic. Acar.). Residues by extraction from plants with benzene, oxidation to the sulfone, nitration, colour reaction with sodium methylate, and colorimetric determination (J. T. Martin & R. F. Batt Annu. Rep. Long Ashton Res. Stat. 1955, 106–110, partly by the method of H. Niessen & H. Frehse Gadamer 1969). For a further colorimetric method see H. J. Hardon et al. (J. Sci. Food Agric. 1957, 8, 368–370). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 4 (1965). EU Status (1107/2009) Never notifed to the EU. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >10 000 mg/kg. Skin and eye Slight irritant action on skin and eyes. NOEL A 5 mg/kg concentration can be tolerated for 3 w in the diet of dogs. ADI/RfD (JMPR) 0.01 mg/kg b.w. [1965]. Toxicity Class WHO (a.i.) O 100 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorbromuron ECOTOXICOLOGY: Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In warm-blooded organisms, elimination is as the glucuronic acid conjugate. Soil/Environment Presumably degraded by enzymic hydrolysis. Details PM3, p. 97. chlorbicyclen Insecticide NOMENCLATURE: Common name chlorbicyclen (BSI, E-ISO); chlorbicyclè(ne) ((m) F-ISO) IUPAC name 1,2,3,4,7,7-hexachloro-5,6-bis(chloromethyl)-8,9,10-trinorborn-2-ene Chemical Abstracts name 1,2,3,4,7,7-hexachloro-5,6-bis(chloromethyl) bicyclo[2.2.1]hept-2-ene CAS RN [2550–75–6] Development codes Hercules 426 Smiles code ClCC1C(CCl)C2(Cl)C(=C(Cl)C1(Cl)C2(Cl)Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 397.8 M.f. C 9 H 6 Cl 8 COMMERCIALISATION: History Insecticide introduced by Hercules Inc. Agrochemicals (and later Nor-Am). PRODUCTS: Discontinued products ‘Alodan’* (Hercules). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O chlorbromuron Herbicide HRAC C2 WSSA 7 NOMENCLATURE: Common name chlorobromuron ((m) F-ISO); chlorbromuron (BSI, E-ISO, WSSA, ex-ANSI) IUPAC name 3-(4-bromo-3-chlorophenyl)-1-methoxy-1-methylurea Chemical Abstracts name N′-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea CAS RN [13360–45–7] EC no 236–411–9 Development codes C 6313 (Ciba) Br Cl NH C NOCH 3 O CH 3 Supplementary Entries – Extended chlorbromuron 101 Smiles code CON(C)C(=O)Nc1ccc(Br)c(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 293.5 M.f. C 9 H 10 BrClN 2 O 2 Form Colourless powder. M.p. 95–97 °C V.p. 0.053 mPa (20 °C) K ow logP = 2.9 Henry 4 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.69 (20 °C) Solubility In water 35 mg/l (20 °C). In acetone 460, dichloromethane 170, hexane 89, benzene 72, isopropanol 12 (all in g/kg, 20 °C). Stability Slowly hydrolysed in neutral, slightly acidic, and slightly alkaline media. COMMERCIALISATION: History Herbicide reported by D. H. Green et al. (Proc. Br. Weed Control Conf., 8th, 1966, 2, 363). Introduced by Ciba AG (later Syngenta AG). Patents BE 662268; GB 965313 APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective herbicide, absorbed by the roots and leaves. Uses Herbicide suitable for: pre-emergence use on carrots, peas, potatoes, soya beans, and sunfowers, at 1.0–2.5 kg/ha; post-emergence use on carrots and transplanted celery, at 0.75–1.5 kg/ha. Phytotoxicity A number of crops may be injured by pre-emergence applications, e.g. rice, beet, okra, fax, cucurbits, tomatoes, strawberries, etc. Formulation types WP. PRODUCTS: Discontinued products ‘Maloran’* (Syngenta). ANALYSIS: Product analysis by glc. Residues determined by hydrolysis to 4-bromo-3-chloroaniline, a derivative of which is determined by colorimetry, or by glc with ECD (G. Voss, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 569). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats >2000, rabbits >10 000 mg/kg. Not a skin or eye irritant. Inhalation LC 50 (6 h) for rats >1.05 mg/l air. NOEL (90 d) for rats 316 mg/kg diet (21.0 mg/kg daily), dogs >316 mg/ kg diet (10.5 mg/kg daily). Toxicity Class WHO (a.i.) III (company classifcation); WHO Recommended Classifcation gave U (now O) EPA (formulation) IV ECOTOXICOLOGY: Birds Dietary LC 50 (10 d) for pheasants and mallard ducks >10 250 mg/kg diet. Fish LC 50 (96 h) for rainbow trout 5, bluegill sunfsh 5, crucian carp 8 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Plants In plants, metabolism involves demethylation and deamination-decarboxylation to the corresponding aniline molecule. Soil/Environment In biologically active soils, DT 50 8–28 w; strongly bound to soil (K oc 908), indicating low leaching potential. In water, stable against abiotic degradation, but in biologically active systems, DT 50 4–11 w. Details PM12, Entry 127. 102 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorbufam chlorbufam Herbicide NOMENCLATURE: Common name chlorbufame ((m) F-ISO); chlorbufam (BSI, E-ISO); BIPC (JMAF) IUPAC name 1-methylprop-2-ynyl 3-chlorocarbanilate; 1-methylprop-2-ynyl 3-chlorophenylcarbamate Chemical Abstracts name 1-methyl-2-propynyl (3-chlorophenyl)carbamate CAS RN [1967–16–4] Smiles code CC(OC(=O)Nc1cccc(Cl)c1)C#C PHYSICAL CHEMISTRY: Mol. wt. 223.7 M.f. C 11 H 10 ClNO 2 Form Colourless crystals. M.p. 45–46 °C V.p. 2.1 mPa (20 °C) Henry 8.70 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.22 (tech.) Solubility In water 540 mg/l (20 °C). In methanol 286, acetone 280, ethanol 95 (all in g/kg, 20 °C). Stability Unstable in strongly acidic and alkaline media (l>pH>13). Changes colour when exposed to light. Alcohols may cause trans-esterifcation. Stable up to 40 °C. COMMERCIALISATION: History Herbicide reported by A. Fischer (Z. Pfanzenkr. Pfanzenpathol. Pfanzenschutz, 1960, 67, 577). Introduced by BASF AG. Patents DE 1034912; DE 1062482 Manufacturers BASF APPLICATIONS: Biochemistry Inhibits photosynthesis. Cell division inhibitor Uses Was normally used in combination with other herbicides for pre-emergence control of grasses and broad-leaved weeds in onions, leeks, garlic, shallots, carrots, beet, spinach, sunfowers, and bulb fowers. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘BiPC’* (BASF); Discontinued mixtures ‘Alipur’* (+ cycluron) (BASF). ANALYSIS: Product analysis by acid hydrolysis to 3-chloroaniline, determined by titration. Residues determined by hydrolysis and colorimetry of the resulting 3-chloroaniline or by glc (Analyt. von Pf. in Wasser, p. 67) TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2500 mg/kg. Skin and eye Mild skin irritant (rabbits). NOEL (4 mo) for rats 400 mg/kg diet. Other Acute i.p. LD 50 for mice 250 mg/kg. NH C O O CH 3 CH C CH Cl Supplementary Entries – Extended chlordecone 103 Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Bees Not toxic to bees. Details PM10, Entry 116. chlordecone Insecticide NOMENCLATURE: Common name chlordecone (BSI, E-ISO, (m) F-ISO) IUPAC name perchloropentacyclo[5.3.0.02,6.03,9.04,8]decan-5-one Chemical Abstracts name 1,1a,3,3a,4,5,5,5a,5b,6-decachlorooctahydro-1,3,4- metheno-2H-cyclobuta[cd]pentalen-2-one CAS RN [143–50–0] EC no 205–601–3 Development codes GC-1189 Smiles code ClC1(C2(Cl)C3(Cl)C 14 Cl)C5(Cl)C(=O)C4(Cl)C(Cl)(C25Cl)C3(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 490.6 M.f. C 10 Cl 10 O M.p. Decomposes (without melting) around 350 °C V.p. 4 × 10 –2 mPa (25 °C) Stability Wide stability to alkalis. Decomposed by strong mineral acids. COMMERCIALISATION: History Insecticide introduced by Allied Chemical Corp., Agricultural Div. (later Hopkins Ltd). APPLICATIONS: Biochemistry Interferes with oxidative phosphorylation. Mode of action Insecticide with stomach action and weak contact action. Secondary fungicidal effects. Uses Insecticidal control of cockroaches and ants. Formulation types RB; WP. PRODUCTS: Discontinued products ‘Kepone’* (Hopkins). ANALYSIS: Product by gc determination as for residues, or by i.r. spectrophotometric determination (6.1 μm and 2.8–3.1 μm) according to E. E. Gilbert et al. (J. Agric. Food Chem. 1966, 14, 115–116). Residues in cereals by gc with a tritium ECD, see J. Burke & L. Giuffrida (J. Assoc. Off. Anal. Chem. 1964, 47, 326–342); also with microcoulometric detection and clean-up on aluminium oxide, see D. Firestone et al. (ibid. 1963, 46, 384–396) and J. F. Thompson et al. (with ECD) (ibid. 1969, 52,1263–1272). See also Man. Pestic. Residue Anal., 247. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 43 (1984). HSG 41 (1990). ICSC.432 (2003). IARC 20 (1979). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEC, as amended by Regulation 850/2004. MAMMALIAN TOXICOLOGY: IARC Class 2B 104 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlordimeform; chlordimeform hydrochloride Oral Acute oral LD 50 for albino rats 126–132, rabbits 71, dogs 250 mg/kg (5% solution in corn oil). Skin and eye Dermal LD 50 for male rabbits 450 mg/kg. NOEL LD 50 for long- term feeding 14 mg/kg b.w. daily. Toxicity Class WHO (a.i.) O EC Classifcation T; R24/25| R40| N; R50, R53 ECOTOXICOLOGY: Fish Toxic to fsh. Details PM5, p. 94. chlordimeform; chlordimeform hydrochloride Acaricide, insecticide NOMENCLATURE: Common name chlorophenamidine (JMAF); chlorodimeform (New Zealand); chlordimeform (BSI, E-ISO, ANSI); chlordimé(forme) ((m) F-ISO) IUPAC name N 2 -(4-chloro-o-tolyl)-N1,N1-dimethylformamidine Chemical Abstracts name N′-(4-chloro-2-methylphenyl)-N,N-dimethylmethanimidamide CAS RN [6164–98–3] chlordimeform; [19750–95–9] chlordimeform hydrochloride EC no 228–200–5 chlordimeform; 243–269–1 chlordimeform hydrochloride Development codes Schering 36 268; C 8514 (Ciba-Geigy) PHYSICAL CHEMISTRY: Composition Tech. is >96%. Mol. wt. 196.7; (hydrochloride 233.1) M.f. C 10 H 13 ClN 2 ; (hydrochloride C 10 H 14 Cl 2 N 2 ) Form Colourless crystals. M.p. 32 °C; (hydrochloride 225–227 °C (decomp.)) B.p. 163–165 °C /14 mmHg V.p. Base: 48 mPa (20 °C) K ow logP = 1.8 (base), 0.201 (hydrochloride) Henry 3.78 × 10 –2 Pa m 3 mol –1 (20 °C, calc.) S.g./density 1.10 (30 °C) Solubility Base: In water 250 mg/l (20 °C). In acetone, benzene, chloroform, ethyl acetate, hexane, methanol >200 g/l (20 °C). Hydrochloride: In water >500 g/l. In benzene, hexane 1, chloroform 10–20, methanol >300 (all in g/l). Stability Hydrolysed frst to 4-chloro-o- tolylformamide and then to 4-chloro-o-toluidine; DT 50 112 d (pH 5), 7.5 d (pH 7), 0.5 d (pH 9, 20 °C) (ARS PPD). COMMERCIALISATION: History Acaricide reported by V. Dittrich (J. Econ. Entomol., 1966, 59, 889). Introduced by Ciba AG (later Ciba-Geigy AG) and Schering AG. Patents GB 1039930; DE 1172081; US 3378437 APPLICATIONS: Mode of action Systemic acaricide and insecticide with contact, stomach, and respiratory action. Uses Chlordimeform controls eggs and larvae of Heliothis spp. on cotton at 150–225 g/ha. Also effective against the eggs and early instars of other Lepidoptera, e.g. Chilo suppressalis, Cydia pomonella, Spodoptera littoralis, Trichoplusia ni, at 0.2–1.0 kg/ha, and is effective against mites and their eggs. Phytotoxicity Injury may occur on some Supplementary Entries – Extended chloreturon 105 ornamentals, tomatoes, tobacco, cucurbits, brassicas, lettuce, beans, capsicums, aubergines, and maize. Russetting may occur with pears. Formulation types EC; SP. PRODUCTS: Discontinued products ‘Fundal’* (as base or hydrochloride, depending on formulation) (Schering); ‘Galecron’* (base) (Ciba-Geigy); ‘Spanon’* (Nihon Nohyaku); ‘Spanone’* (Schering). ANALYSIS: Product analysis by acid-base titration or by glc (CIPAC Handbook, 1988, D, 28; AOAC Methods 18th Ed., 985.05; J. Assoc. Off. Anal. Chem., 1985, 68, 371; G. Voss et al., Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 211). Residues determined by glc of a derivative (idem, ibid.; H. Geissbühler et al., J. Agric. Food Chem., 1971, 19, 365). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 199 (1998). JMPR Evaln. I 48 (1986); JMPR Evaln. II 52 (1987). ICSC.124 (base; 1994); ICSC.125 (hydrochloride; 1994). IARC 30 (1983). MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Chlordimeform: Acute oral LD 50 for rats 340, rabbits 625 mg/kg. Chlordimeform hydrochloride: Acute oral LD 50 for rats 355 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >4000 mg hydrochloride/kg. Slight skin irritant (rabbits). NOEL (2 y) for rats 0.1 mg/kg daily, for dogs 6.25 mg/kg daily. ADI/RfD (JMPR) Temporary ADI withdrawn [1987]; (EPA) 0.001 mg/kg b.w. [1987]. Toxicity Class WHO (a.i.) II EC Classifcation R40| Xn; R21/22| N; R50, R53 (chlordimeform): R40| Xn; R22| N; R50, R53 (chlordimeform hydrochloride) PIC Yes. ECOTOXICOLOGY: Fish LC 50 (96 h) for trout 7.1, barbel 4.5, bluefll sunfsh 1 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, undergoes N-demethylation and hydrolysis. The principal metabolite is p-chloro-o-toluidine. Plants Metabolism in plants is similar to that in mammals. Soil/Environment In soil, degradation is similar to metabolism in mammals. Details PM8, Entry 02270. chloreturon Herbicide NOMENCLATURE: Common name chloreturon (BSI, E-ISO, (m) F-ISO) IUPAC name 3-(3-chloro-4-ethoxyphenyl)-1,1-dimethylurea Chemical Abstracts name N′-(3-chloro-4-ethoxyphenyl)-N,N-dimethylurea CAS RN [20782–58–5] Smiles code CCOc1ccc(NC(=O)N(C)C)cc1Cl 106 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorfenac; chlorfenac-sodium PHYSICAL CHEMISTRY: Mol. wt. 242.7 M.f. C 11 H 15 ClN 2 O 2 COMMERCIALISATION: History Herbicide reported by A. Aamisepp (Proc. Swed. Weed Conf., 1977, 18, F9-F13). Evaluated by Hoechst AG. chlorfenac; chlorfenac-sodium Herbicide NOMENCLATURE: Common name chlorfenac (BSI, E-ISO, (m) F-ISO); fenac (WSSA) IUPAC name (2,3,6-trichlorophenyl)acetic acid Chemical Abstracts name 2,3,6-trichlorobenzeneacetic acid CAS RN [85–34–7] chlorfenac; [2439–00–1] chlorfenac-sodium EC no 201–599–3 PHYSICAL CHEMISTRY: Mol. wt. 239.5; (sodium salt 261.5) M.f. C 8 H 5 Cl 3 O 2 ; (sodium salt C8H4Cl3NaO 2 ) Form Colourless solid. M.p. 156 °C V.p. 1100 mPa (100 °C) Solubility In water 200 mg/l (28 °C). Soluble in most organic solvents. Stability Photolytically decomposed by uv light. Very stable in acidic media. Forms water-soluble salts with alkalis. pKa 3.70 (ARS PPD) COMMERCIALISATION: History Herbicide introduced by Amchem Products Inc. (later Rhône-Poulenc Agrochimie) and Hooker Chemical Corp. Patents GB 860310 APPLICATIONS: Mode of action Systemic herbicide, absorbed primarily by roots, with translocation. Uses Usually applied as the sodium salt, it was used to control annual grasses, broad-leaved weeds, Elymus repens, Convolvulus arvensis and other perennial weeds in industrial and other non-crop situations at rates up to 18 kg a.e./ha. Also used pre-em. at 2.8–3.4 kg a.e./ha for weed control in sugar cane. Formulation types SL . PRODUCTS: Discontinued products ‘Fenac’* (Amchem); ‘Fenatrol’* (sodium salt) (Amchem). ANALYSIS: Product analysis by glc. Residues determined by glc of suitable derivatives (G. Yip, J. Assoc. Off. Anal. Chem., 1972, 45, 367). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 576–1780 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 1440–3160 mg/kg. NOEL In 2 y feeding trials, rats receiving 2000 mg/kg diet showed no ill-effect. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| N; R51, R53 ECOTOXICOLOGY: Fish Not toxic to fsh when used as recommended. Bees Not toxic to bees. Supplementary Entries – Extended chlorfenethol 107 ENVIRONMENTAL FATE: Soil/Environment Does not leach. In soil, undergoes slow microbial degradation and persists for c. 1–2 y. Details PM8, Entry 02300. chlorfenazole Fungicide NOMENCLATURE: Common name chlorfé(nazole) ((m) F-ISO); chlorfenazole (BSI, E-ISO) IUPAC name 2-(2-chlorophenyl)benzimidazole Chemical Abstracts name 2-(2-chlorophenyl)-1H-benzimidazole CAS RN [3574–96–7] Development codes CUR 616 Smiles code Clc1ccccc1c2nc3ccccc3[nH]2 PHYSICAL CHEMISTRY: Mol. wt. 228.7 M.f. C 13 H 9 ClN 2 COMMERCIALISATION: History Fungicide introduced by Celamerck GmbH & Co., KG (later Shell Agrar GmbH). chlorfenethol Acaricide NOMENCLATURE: Common name chlorfenethol (BSI, E-ISO, (m) E-ISO, ESA); BCPE (JMAF) IUPAC name 1,1-bis(4-chlorophenyl)ethanol Chemical Abstracts name 4-chloro-α-(4-chlorophenyl)-α-methylbenzenemethanol Other names DMC; DCPC CAS RN [80–06–8] EC no 201–246–3 Smiles code CC(O)(c1ccc(Cl)cc1)c2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Composition May contain the 2,4’- isomer. Mol. wt. 267.2 M.f. C 14 H 12 Cl 2 O Form Colourless crystals. M.p. 69.5–70 °C V.p. Not known exactly; said to be 4 to 8 times more volatile than DDT. Solubility Practically insoluble in water. Readily soluble in most organic solvents, particularly polar ones. Stability Stable to alkalis, but unstable to strong acids. Heating leads to dehydration. COMMERCIALISATION: History Acaricide reported by O. Grummitt (Science, 1950, 111, 361). Introduced by Sherwin-Williams & Co. and later by Nippon Soda Co. Ltd. Patents US 2430586. APPLICATIONS: Mode of action Non-systemic acaricide with predominantly ovicidal activity, having slow uptake and retaining effectiveness over a long period. Uses Control of spider mites (in the 108 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorfenprop; chlorfenprop-methyl open and under glass) in fruit, vegetables, vines, hops, cotton, and ornamental cultivation. Formulation types WP. PRODUCTS: Discontinued products ‘Dimite’* (Sherwin-Williams); ‘Qikron’* (Nippon Soda); Discontinued mixtures ‘Milbex’* (+ chlorfensulphide) (Nippon Soda); ‘Mitran’* (+ chlorfenson) (Nippon Soda). ANALYSIS: Product analysis (1) separation from chlorfensulfde in commercial mixed formulations by column chromatography on aluminium oxide and gravimetric determination. (2) uv spectrophotometry in isooctane solution at 240 and 260 nm (Anal. Insectic. Acar., p. 432–435). Residues by reaction with p-toluenesulfonic acid to give 1,1-bis(4-chlorophenyl)ethylene, and determination by gc with ECD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 926–1391 mg/kg. NOEL Rats tolerated 1000 mg/kg diet fed for 10 d (L. Peters, Proc. Soc. Exp. Biol. Med., 1947, 72, 304). Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| N; R51, R53 ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 1.8 mg/l. Bees Not toxic to bees. Details PM6, p. 97. chlorfenprop; chlorfenprop-methyl Herbicide NOMENCLATURE: Common name chlorfenprop (BSI, E-ISO, (m) F-ISO) IUPAC name (±)-2-chloro-3-(4-chlorophenyl)propionic acid Chemical Abstracts name (±)-α,4-dichlorobenzenepropanoic acid CAS RN [14437–20–8] chlorfenprop (racemate), formerly [59604–11–4]; [59604– 10–3] chlorfenprop-methyl (racemate) EC no 238–413–5 chlorfenprop-methyl Development codes Bayer 70 533 PHYSICAL CHEMISTRY: Mol. wt. 219.1; (methyl ester 233.1) M.f. C 9 H 8 Cl 2 O 2 ; (methyl ester C 10 H 10 Cl 2 O 2 ) Form Colourless liquid (ester); light brown liquid (tech. ester). M.p. >–20 °C (ester) B.p. 110–113 °C /0.1 mmHg (ester) V.p. 930 mPa (50 °C) (ester) S.g./density 1.30 (20 °C, tech. ester) Solubility In water 40 mg/l (20 °C, ester). Soluble in acetone, aromatic hydrocarbons, diethyl ether and fatty oils. COMMERCIALISATION: History Herbicide reported by L. Eue (Z. Pfanzenkr. Pfanzenpathol. Pfanzenschutz, 1968, Sonderheft IV, 211). Only the (–)- enantiomer is herbicidal (T. Schmidt et al., Z. Naturforsch. C. Biosci., 1976, 31C, 252). Chlorfenprop-methyl introduced by Bayer AG. Patents GB 1077194, FR 1476247. Supplementary Entries – Extended chlorfenson 109 APPLICATIONS: Mode of action Contact herbicide. Uses For post-emergence control of wild oats, in cereals (not oats), fodder crops, peas and sugar beet; applied at 4 kg/ha. Only the (-)- enantiomer is herbicidal (T. Schmidt et al., Z. Naturforsch. C. Biosci., 1976, 31C, 252). Formulation types EC. PRODUCTS: Discontinued products ‘Bidisin’* (Bayer). ANALYSIS: Product analysis is by glc. Residues are also determined by glc (H. J. Jarczyk, Pfanz. Nachr.- Bayer (Engl. Ed.) 1968, 21,360). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R21/22| N; R50, R53 (chlorfenprop-methyl) Details PM7, Entry 02330. chlorfenson Acaricide NOMENCLATURE: Common name ovatran (Argentina); ephirsulphonate* (former exception, USSR); CPCBS (JMAF); chlorofé(nizon) ((m) France); chlorfenson (BSI, E-ISO, (m) F-ISO); ovex (ANSI, Canada) IUPAC name 4-chlorophenyl 4-chlorobenzenesulfonate Chemical Abstracts name 4-chlorophenyl 4-chlorobenzenesulfonate Other names chlorfenizon CAS RN [80–33–1] EC no 201–270–4 Development codes K 6451 (Dow) Smiles code Clc1ccc(OS(=O)(=O)c2ccc(Cl)cc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 303.2 M.f. C 12 H 8 Cl 2 O 3 S Form Colourless crystalline solid, with a characteristic odour; (tech. is a colourless to tan faky solid). M.p. 86.5 °C; (tech., c. 80 °C) V.p. Negligible (25 °C) Solubility Practically insoluble in water (25 °C). In acetone 1300, ethanol 10, xylene 780 (all in g/kg, 25 °C). Stability Hydrolysed by alkali. COMMERCIALISATION: History Acaricide reported by E. E. Kenaga & R. W. Hummer (J. Econ. Entomol., 1949, 42, 996). Introduced by Dow Chemical Co. (later DowElanco). Patents US 2528310 APPLICATIONS: Mode of action A non-systemic acaricide with contact and stomach action and long residual ovicidal activity. Uses Effective against mites of citrus and other fruit, ornamentals and vegetable crops at 17–32 g/100 l. Phytotoxicity Russetting may occur with apples and 110 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorfensulphide pears. Hops may be injured, and leaf drop may occur on roses. Formulation types WP. PRODUCTS: Discontinued products ‘Ovitox’* (Sipcam Phyteurop); ‘Ovotran’* (Dow); ‘Sappiran’* (Nippon Soda); ‘Trichlorfenson’* (Bourgeois); Discontinued mixtures ‘Erysit Super’* (+ prothoate) (Schering); ‘Fac Super’* (+ prothoate) (Sopra); ‘Mitran’* (+ chlorfenethol) (Nippon Soda); ‘Naftil’* (+ carbaryl) (Pepro). ANALYSIS: Product analysis by alkaline hydrolysis and back titration (CIPAC Handbook, 1970, 1, 213; FAO Plant Prot. Bull., 1964, 12, 17). Residues determined by glc or by colorimetry of a derivative produced after alkaline hydrolysis (A. H. Kutschinski & E. N. Luce, Anal. Chem., 1952, 24, 1188; F. A. Gunther & L. R. Jepson, J. Econ. Entomol., 1954, 47, 1027). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 4 (1965). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for ratsc. 2000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >10 000 mg/kg. It may cause skin irritation. NOEL In 130 d feeding trials, no effect was observed on rats receiving 300 mg/kg diet. ADI/RfD (JMPR) 0.01 mg/kg b.w. [1965]. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| Xi; R38| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for Japanese quail 4600, chickens 3780 mg/kg. Fish LC 50 (48 h) for carp 3.2 mg/l. Bees Not toxic to bees. Details PM8, Entry 02340. chlorfensulphide Acaricide NOMENCLATURE: Common name CPAS (JMAF); chlorfensulfde ((m) F-ISO); chlorfensulphide (BSI, E-ISO) IUPAC name 4-chlorophenyl 2,4,5-trichlorobenzenediazosulfde Chemical Abstracts name [(4-chlorophenyl)thio](2,4,5-trichlorophenyl)diazene CAS RN [2274–74–0] Smiles code Clc1ccc(SN=Nc2cc(Cl)c(Cl)cc2Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 352.1 M.f. C 12 H 6 Cl 4 N 2 S M.p. 123.5 °C V.p. Very low at room temperature Solubility Practically insoluble in water. Readily soluble in acetone, soluble in benzene. Stability Extremely stable to acids and bases. COMMERCIALISATION: History Introduced as a component of an acaricide by Nippon Soda Co., Ltd. APPLICATIONS: Mode of action Non-systemic acaricide with contact action. Uses Control of spider mites (in the open and under glass) in fruit, vines, hops, and ornamental cultivation. Supplementary Entries – Extended chlorfuren; chlorfuren-methyl 111 PRODUCTS: Discontinued mixtures ‘Milbex’* (+ chlorfenethol) (Nippon Soda). ANALYSIS: Product: separation of the components of the commercial product by column chromatography on aluminium oxide and determination of chlorfensulfde spectrophotometrically at 460 nm Residues by extraction and clean-up by column chromatography, as above, and determination by gc with ECD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 4000 mg/kg. NOEL In rats fed a diet containing 400 mg/kg for 6 mo, no organ damage is produced and survival rate is unaffected; NOEL 800 mg/kg. Toxicity Class WHO (a.i.) O ECOTOXICOLOGY: Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In warm-blooded animals, transformed to the 2,4,4’,5-tetrachlorodiphenylsulfde, with some further oxidation to the corresponding sulfone. Plants In plants, it is rapidly transformed to the 2,4,4’,5-tetrachlorodiphenylsulfde. Details PM4, p. 101. chlorfurazole Herbicide NOMENCLATURE: Common name chlorfurazole (BSI, E-ISO, (m) F-ISO) IUPAC name 4,5-dichloro-2-trifuoromethylbenzimidazole Chemical Abstracts name 4,5-dichloro-2-(trifuoromethyl)-1H-benzimidazole CAS RN [3615–21–2] Development codes NC 3363 Smiles code FC(F)(F)c1nc2c(Cl)c(Cl)ccc2[nH]1 PHYSICAL CHEMISTRY: Mol. wt. 255.0 M.f. C 8 H 3 Cl 2 F 3 N 2 COMMERCIALISATION: History Herbicide evaluated by Fisons PLC (later Schering Agriculture). chlorfuren; chlorfuren-methyl Plant growth regulator NOMENCLATURE: Common name chlorfuren (BSI, E-ISO); chlorfurè(ne) ((m) F-ISO) IUPAC name 2-chlorofuorene-9-carboxylic acid 112 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlornitrofen Chemical Abstracts name 2-chloro-9H-fuorene-9-carboxylic acid CAS RN [24539– 66–0] chlorfuren; [22909–50–8] chlorfuren-methyl Development codes IT-5732 (chlorfuren-methyl) PHYSICAL CHEMISTRY: Mol. wt. 244.7; (methyl ester 258.7) M.f. C 14 H 9 ClO 2 ; (methyl ester C 15 H 11 ClO 2 ) COMMERCIALISATION: History Plant growth regulator introduced by E. Merck (later Shell Agrar GmbH). chlornitrofen Herbicide NOMENCLATURE: Common name chlornitrofen (BSI, E-ISO); chlornitrofè(ne) (F-ISO); CNP (JMAF) IUPAC name 4-nitrophenyl 2,4,6-trichlorophenyl ether Chemical Abstracts name 1,3,5-trichloro-2-(4-nitrophenoxy)benzene CAS RN [1836–77–7] Development codes MO-338 Smiles code [O-][N+](=O)c1ccc(Oc2c(Cl)cc(Cl)cc2Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 318.5 M.f. C 12 H 6 Cl 3 NO 3 Form Pale yellow crystals. M.p. 107 °C V.p. 3.2 mPa (20 °C) K ow logP = 5.09 S.g./density 1.623 (23 °C) Solubility In water 0.25 mg/l (25 °C). In xylene 360 g/kg (25 °C). Stability Stable under neutral conditions up to 250 °C. COMMERCIALISATION: History Herbicide introduced in Japan (1966) by Mitsui Toatsu Chemicals, Inc. (later Mitsui Chemicals, Inc.). Patents GB 1016648; US 3316080; IT 723364 Manufacturers Mitsui Toatsu; Sinon APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. Mode of action Selective contact herbicide. Uses Control of annual weeds in rice. Formulation types GR; EC. PRODUCTS: Discontinued products ‘Mo’* (Mitsui Toatsu). ANALYSIS: Product and residue analysis by glc with ECD (Noyaku-Seisan Gijutsu 1971, 23, 1–14). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice 10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >10 000 mg/kg. Inhalation LC 50 (4 h) for rats >0.52 mg/l air. NOEL (2 y) for Cl O NO 2 Cl Cl Supplementary Entries – Extended chlorobenzilate 113 rats 0.61, mice 9.5 mg/kg diet. Toxicity Class WHO (a.i.) U EPA (formulation) IV ECOTOXICOLOGY: Birds Acute oral LD 50 for pheasants 2680 mg/kg. Fish LC 50 (48 h) for carp >40, killifsh >100 mg/l. Daphnia LC 50 (3 h) >40 mg/l. Details PM10, Entry 126. chlorobenzilate Acaricide NOMENCLATURE: Common name chlorobenzilate (BSI, E-ISO, (m) F-ISO, ESA, JMAF) IUPAC name ethyl 4,4′-dichlorobenzilate Chemical Abstracts name ethyl 4-chloro-α-(4-chlorophenyl)-α-hydroxybenzeneacetate CAS RN [510–15–6] EC no 208–110–2 Development codes G 23 992 Smiles code CCOC(=O)C(O)(c1ccc(Cl)cc1)c2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 325.2 M.f. C 16 H 14 Cl 2 O 3 Form Colourless solid. M.p. 36–37.5 °C B.p. 156–158 °C /0.07 mmHg V.p. 0.12 mPa (20 °C) K ow logP = 4.58 Henry 3.90 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.2816 (20 °C) Solubility In water 10 mg/l (20 °C). Readily soluble in most organic solvents, e.g. in acetone, dichloromethane, methanol, toluene 1000, n-octanol 700, hexane 600 (all in g/kg, 20 °C). Stability Hydrolysis DT 50 7 d (pH 9), 3 d (pH 7), stable (pH 5) (all 25 °C) (ARS PPD). COMMERCIALISATION: History Acaricide reported by R. Gasser (Experientia, 1952, 8, 65). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). Patents BE 511234; GB 705037 Manufacturers Makhteshim-Agan APPLICATIONS: Mode of action Non-systemic acaricide with contact action and with little insecticidal action. Uses Used for control of many species of phytophagous mites on pome fruit, citrus fruit, vines, soya beans, cotton, tea, and vegetables at 1.0–1.5 kg/ha. Also used for control of bee mites in beehives. Phytotoxicity Peaches, plums, and some varieties of apple may be injured. Russetting is possible with pears. Formulation types EC; WP. Compatibility Incompatible with highly alkaline materials. PRODUCTS: Discontinued products ‘Acaraben’* (USA) (Ciba-Geigy); ‘Akar’* (Ciba-Geigy); ‘Folbex’* (Ciba). Cl C CO 2 CH 2 CH 3 OH Cl 114 The Pesticide Manual Sixteenth Edition © BCPC 2012 1-chloro-2,4-dinitronaphthalene ANALYSIS: Product analysis by glc with FID (E. Bartsch et al., Residue Rev., 1971, 39, 1; A. Margot & K. Stammbach, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 2, 65; CIPAC Handbook, 1998, H, 81; AOAC Methods, 18th Ed., 971.08). Residues determined by glc with MCD or ECD (Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1972, 6, 319; G. Formica et al., Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1975, 40, 1135; E. Bartsch et al., loc. cit.; Pestic. Anal. Manual 1979, I, 201-A, 201-G; 1979, II; R. Mestres et al., Trav. Soc. Pharm. Montpellier, 1979, 39, 323). In drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 35 (1980). IARC 30 (1983). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for rats 2784–3880 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and rabbits >10 000 mg/kg. Irritating to eyes; non-irritating to skin (rabbits). NOEL (2 y) for rats 40 mg/kg diet (c 2.7 mg/kg daily); for dogs 500 mg/kg diet (c. 16.0 mg/kg daily). ADI/RfD (JMPR) 0.02 mg/kg b.w. [1980]; (EPA) cRfD 0.02 mg/kg b.w. [1989]. Water GV Excluded from GV derivation (U). Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R22| N; R50, R53 PIC Yes. ECOTOXICOLOGY: Birds Practically non-toxic to birds. Fish LC 50 for rainbow trout 0.6, bluegill sunfsh 1.8 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In rats, following oral administration, the principal metabolites identifed were p,p’-dichlorobenzilic acid, p,p’-dichlorobenzylhydrol, p-chlorobenzoic acid, and p,p’-dichlorobenzophenone. Details PM10, Entry 128. 1-chloro-2,4-dinitronaphthalene Fungicide NOMENCLATURE: IUPAC name 1-chloro-2,4-dinitronaphthalene (I) Chemical Abstracts name (I) CAS RN [2401–85–6] Smiles code [O-][N+](=O)c1cc([N+](=O)[O-])c2ccccc2c1Cl PHYSICAL CHEMISTRY: Mol. wt. 252.6 M.f. C 10 H 5 ClN 2 O 4 COMMERCIALISATION: History Fungicide. Supplementary Entries – Extended chloromethiuron 115 chloromebuform Acaricide NOMENCLATURE: Common name chloromebuform (BSI, E-ISO); chloromé(buforme) ((m) F-ISO) IUPAC name N 1 -butyl-N 2 -(4-chloro-o-tolyl)-N 1 -methylformamidine Chemical Abstracts name N-butyl-N′-(4-chloro-2-methylphenyl)-N- methylmethanimidamide; N-butyl-N′-(4-chloro-o-tolyl)-N′-methylformamidine CAS RN [37407–77–5] Development codes CGA 22 598 Smiles code CCCCN(C)C=Nc1ccc(Cl)cc1C PHYSICAL CHEMISTRY: Mol. wt. 238.8 M.f. C 13 H 19 ClN 2 COMMERCIALISATION: History Acaricide evaluated by Ciba-Geigy AG. PRODUCTS: Discontinued products ‘Ektomin’* (Ciba-Geigy). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O chloromethiuron Ixodicide NOMENCLATURE: Common name chloromethiuron (BSI, E-ISO, (m) F-ISO) IUPAC name 3-(4-chloro-o-tolyl)-1,1-dimethyl(thiourea) Chemical Abstracts name N′-(4-chloro-2-methylphenyl)-N,N-dimethylthiourea CAS RN [28217–97–2] Development codes CGA 13 444; C-9140 Smiles code CN(C)C(=S)Nc1ccc(Cl)cc1C PHYSICAL CHEMISTRY: Mol. wt. 228.7 M.f. C 10 H 13 ClN 2 S Form Colourless crystals. M.p. 175 °C V.p. 0.0011 mPa (20 °C) Henry 5.03 × 10 –6 Pa m 3 mol –1 (calc.) S.g./density 1.34 (20 °C) Solubility In water 50 mg/l (20 °C). In acetone 37, dichloromethane 40, hexane 0.05, isopropanol 5 (all in g/kg, 20 °C). Stability Slowly hydrolysed, DT 50 c. 1 y at 5<pH<9. COMMERCIALISATION: History Ixodicide reported by M. von Orelli et al. (Proc. World Vet. Congr., 20th, 1975, p. 659). Introduced by Ciba-Geigy AG. Patents BE 678543; GB 1138714 Cl CH 3 NHCSN(CH 3 ) 2 116 The Pesticide Manual Sixteenth Edition © BCPC 2012 3-(4-chlorophenyl)-5-methylrhodanine APPLICATIONS: Uses Controls Ixodidae including strains resistant to other ixodicides. Used on cattle, sheep, horses and dogs in plunge dips at 1.8 g/l. Formulation types SC. PRODUCTS: Discontinued products ‘Dipofene’* (Ciba-Geigy). ANALYSIS: Product analysis by acidimetric titration. Residues determined by glc with ECD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2500 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats >2150 mg/kg. Not irritant to skin; irritant to eyes (rabbits). NOEL (90 d) for rats 10 mg/kg diet (1 mg/kg daily), for dogs 50 mg/kg diet (2 mg/kg daily). Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Fish LC 50 (96 h) for rainbow trout, bluegill sunfsh, carp >49 mg/l. Details PM9, Entry 2640. 1-chloro-2-nitropropane Fungicide NOMENCLATURE: IUPAC name 1-chloro-2-nitropropane (I) Chemical Abstracts name (I) CAS RN [2425–66–3] Development codes FMC 5916 Smiles code CC(CCl)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 123.5 M.f. C 3 H 6 ClNO 2 COMMERCIALISATION: History Fungicide reported by Bushong (Seed Soil Treatment Newslett., 1962, 4, 39). Introduced by FMC Corp. APPLICATIONS: Mode of action Fumigant soil fungicide. PRODUCTS: Discontinued products ‘Lanstan’* (FMC). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.423 (2001). 3-(4-chlorophenyl)-5-methylrhodanine Fungicide, nematicide NOMENCLATURE: IUPAC name 3-(4-chlorophenyl)-5-methylrhodanine; 3-(4-chlorophenyl)-5-methyl-2- thioxo-1,3-thiazolidin-4-one Supplementary Entries – Extended chloropon 117 Chemical Abstracts name 3-(4-chlorophenyl)-5-methyl-2-thioxo-4-thiazolidinone CAS RN [6012–92–6] Development codes N 244 Smiles code CC1SC(=S)N(C1=O)c2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 257.8 M.f. C 10 H 8 ClNOS 2 COMMERCIALISATION: History Fungicide and nematicide developed by Stauffer Chemical Co. 4-chlorophenyl phenyl sulfone Acaricide NOMENCLATURE: IUPAC name 4-chlorophenyl phenyl sulfone Chemical Abstracts name 1-chloro-4-(phenylsulfonyl)benzene CAS RN [80–00–2] Development codes R-242 Smiles code Clc1ccc(cc1)S(=O)(=O)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 252.7 M.f. C 12 H 9 ClO 2 S COMMERCIALISATION: History Acaricide introduced by Stauffer Chemical Co. (later ICI Americas). PRODUCTS: Discontinued products ‘Sulphenone’* (ICI). ANALYSIS: Residues determined by spectrometry (AOAC Methods, 18th Ed., 958.08, see 11th Ed., 29.075–29.081). chloropon Herbicide NOMENCLATURE: Common name chloropon (BSI, E-ISO, (m) F-ISO) IUPAC name 2,2,3-trichloropropionic acid Chemical Abstracts name 2,2,3-trichloropropanoic acid CAS RN [3278–46–4] Smiles code OC(=O)C(Cl)(Cl)CCl PHYSICAL CHEMISTRY: Mol. wt. 177.4 M.f. C 3 H 3 Cl 3 O 2 COMMERCIALISATION: History Herbicide. 118 The Pesticide Manual Sixteenth Edition © BCPC 2012 chloropropylate chloropropylate Acaricide IRAC 12C NOMENCLATURE: Common name chloropropylate (BSI, E-ISO, (m) F-ISO, ANSI, ESA, JMAF) IUPAC name isopropyl 4,4′-dichlorobenzilate Chemical Abstracts name 1-methylethyl 4-chloro-α-(4-chlorophenyl)-α- hydroxybenzeneacetate CAS RN [5836–10–2] Development codes G 24 163 Smiles code CC(C)OC(=O)C(O)(c1ccc(Cl)cc1)c2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 339.2 M.f. C 17 H 16 Cl 2 O 3 Form Colourless crystals. M.p. 73 °C B.p. 148–150 °C /0.5 mmHg V.p. 0.044 mPa (20 °C) Henry 9.95 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.35 (20 °C) Solubility In water 1.5 mg/l (20 °C). In acetone, dichloromethane 700, hexane 50, methanol 300, n-octanol 130, toluene 500 (all in g/l, 20°C). COMMERCIALISATION: History Acaricide reported by F. Chabousson (Phytiatr.-Phytopharm., 1956, 5, 203). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). Patents BE 511234; GB 705037 APPLICATIONS: Biochemistry Inhibitor of oxidative phosphorylation; disruptor of ATP formation. Mode of action Non-systemic acaricide with contact action. Uses At 30–60 g/100 l on cotton, fruit, nuts, ornamentals, sugar beet, tea and vegetables. Formulation types EC. PRODUCTS: Discontinued products ‘Acaralate’* (Ciba); ‘Chlormite’* (Ciba); ‘Rospin’* (Ciba-Geigy). ANALYSIS: Product analysis by glc with FID (E. Bartsch et al., Residue Rev., 1971, 39, 1; CIPAC Handbook, 1998, H, 85; AOAC Methods, 18th Ed., 971.08). Residues determined by glc with MCD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 19 (1972). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg tech./kg. Skin and eye Not irritant to skin and eyes of rabbits. NOEL (2 y) for rats 40 mg/kg diet, for dogs 500 mg/kg diet. ADI/RfD (JMPR) Temporary ADI withdrawn [1972]. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Practically non-toxic to birds. Fish LC 50 (96 h) for bluegill sunfsh 0.66, goldfsh 0.6, rainbow trout 0.45 mg/l. Bees Slightly toxic to honeybees. Details PM8, Entry 02900. Supplementary Entries – Extended chloroxuron 119 2-chlorovinyl diethyl phosphate Insecticide IRAC 1B NOMENCLATURE: IUPAC name 2-chlorovinyl diethyl phosphate Chemical Abstracts name 2-chloroethenyl diethyl phosphate CAS RN [311–47–7] Development codes SD 1836; OS 1836 Smiles code CCOP(=O)(OCC)O/C=C/Cl; without stereochemistry:CCOP(=O)(OCC)OC=CCl PHYSICAL CHEMISTRY: Mol. wt. 214.6 M.f. C 6 H 12 ClO 4 P COMMERCIALISATION: History Insecticide developed by Shell Chemical Co. APPLICATIONS: Biochemistry Cholinesterase inhibitor. chloroxuron Herbicide HRAC C2 WSSA 7; urea NOMENCLATURE: Common name chloroxuron (BSI, E-ISO, (m) F-ISO, ANSI, WSSA, JMAF); chloroxifenidim* (former exception, USSR) IUPAC name 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea Chemical Abstracts name N′-[4-(4-chlorophenoxy)phenyl]-N,N-dimethylurea CAS RN [1982–47–4] Development codes C 1983 Smiles code CN(C)C(=O)Nc1ccc(Oc2ccc(Cl)cc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 290.7 M.f. C15H15ClN 2 O 2 Form Colourless powder. M.p. 151–152 °C V.p. 2.39 × 10 –4 mPa (20 °C) K ow logP = 3.200 Henry 1.88 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.34 (20 °C) Solubility In water 3.7 mg/l (20 °C). In dichloromethane 106, acetone 44, methanol 35, toluene 4 (all in g/kg, 20 °C). Soluble in DMF and chloroform; slightly soluble in benzene and diethyl ether. Stability Decomposed by uv light. No signifcant hydrolysis occurred at 30 °C at pH 1 or pH 13. COMMERCIALISATION: History Herbicide reported (Symp. New Herbic., 3rd, 1961, p. 88). Introduced by Ciba AG (later Ciba-Geigy AG). Patents BE 593743; GB 913383 Cl O NHCON(CH 3 ) 2 120 The Pesticide Manual Sixteenth Edition © BCPC 2012 chloroxuron APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective herbicide, absorbed principally by the roots, but also by the leaves, with limited translocation acropetally. Uses Pre- and post-emergence control of annual broad-leaved weeds and some grasses in peas, beans, carrots, celery, celeriac, onions, leeks, garlic, chives, fennel, parsley, dill, tomatoes, cucurbits, soya beans, strawberries, ornamentals, fruit trees, and conifers. Control of mosses in ornamental and sports turf, on paths and non-crop land, and in glasshouses. Formulation types WP. PRODUCTS: Discontinued products ‘Tenoran’* (Ciba-Geigy). ANALYSIS: Product analysis by determination of the dimethylamine produced by hydrolysis, or by tlc (CIPAC Handbook, 1983, 1B, 1751; G. Voss et al., Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 569; AOAC Methods, 18th Ed., 977.06). Residues determined by hydrolysis to 4-(4-chlorophenoxy)aniline, derivatives of which are measured colorimetrically or by glc with ECD (G. Voss et al., loc. cit.). Alternatively, glc with ECD may be used directly. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 3700, female rats 5400, mice >1000, dogs >10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3000 mg/kg. Slightly irritant to skin and eyes (rabbits). Inhalation LC 50 (6 h) for rats >1.35 mg/l air. NOEL (120 d) for rats 30 mg/kg daily; (90 d) for dogs 400 mg/kg diet (16.7 mg/kg daily). Toxicity Class WHO (a.i.) U EPA (formulation) III ECOTOXICOLOGY: Birds Slightly toxic to birds. Fish LC 50 for bluegill sunfsh 28, rainbow trout >100, crucian carp >150 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Plants In plants, chloroxuron undergoes degradation to the monomethylated and demethylated derivatives, followed by decarboxylation of the phenoxyphenylurea to (4-chlorophenoxy)aniline. Soil/Environment In soil, microbial degradation leads to the monomethylated and demethylated derivatives, and then to the (4-chlorophenoxy)aniline derivative; DT 50 10–100 d. Duration of residual activity in soil isc. 4 months. Details PM9, Entry 2970. Supplementary Entries – Extended chlorphonium chloride 121 2-(4-chloro-3,5-xylyloxy)ethanol Insecticide NOMENCLATURE: IUPAC name 2-(4-chloro-3,5-xylyloxy)ethanol Chemical Abstracts name 2-(4-chloro-3,5-dimethylphenoxy)ethanol CAS RN [5825–79–6] Development codes Experimental Chemotherapeutant 1182 Smiles code Cc1cc(OCCO)cc(C)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 200.7 M.f. C 10 H 13 ClO 2 COMMERCIALISATION: History Insecticide introduced by Union Carbide Corp. (later Rhône-Poulenc Ag.). chloroxynil Herbicide NOMENCLATURE: Common name chloroxynil (BSI, E-ISO, (m) F-ISO) IUPAC name 3,5-dichloro-4-hydroxybenzonitrile (I) Chemical Abstracts name (I) CAS RN [1891–95–8] Smiles code Oc1c(Cl)cc(C#N)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 188.0 M.f. C 7 H 3 Cl 2 NO COMMERCIALISATION: History Herbicide evaluated by May & Baker Ltd (later Rhône-Poulenc Agrochimie). chlorphonium chloride Plant growth regulator NOMENCLATURE: Common name chlorfonium chloride ((m) F-ISO); chlorphonium chloride (BSI, E-ISO) IUPAC name tributyl(2,4-dichlorobenzyl)phosphonium chloride Chemical Abstracts name tributyl[(2,4-dichlorophenyl)methyl]phosphonium chloride CAS RN [115–78–6] EC no 204–105–4 Smiles code [Cl-].CCCC[P+](CCCC)(CCCC)Cc1ccc(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 397.8; 362.3 (chlorphonium ion) M.f. C 19 H 32 Cl 3 P; chlorphonium ion C19H32Cl 2 P Form Colourless crystals. M.p. 114–120 °C V.p. 9.33 × Cl Cl Cl CH 2 P[(CH 2 ) 3 CH 3 ] 3 122 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorphoxim 10-2 mPa (20 °C) Henry 3.52 × 10-8 Pa m 3 mol –1 (20 °C, calc.) Solubility In water 960 g/l (20 °C). In methanol 1030, acetone 200 (both in g/l, 20 °C). Insoluble in diethyl ether and hexane. Stability Stable under normal storage conditions. COMMERCIALISATION: History The chloride was introduced as a plant growth regulator by the Mobil Chemical Co. Patents US 3268323 APPLICATIONS: Uses Used to reduce internodal length in chrysanthemums, geraniums, petunias, and other responsive ornamentals; to increase the breaking of lateral shoots in geraniums and petunias; and to increase the number of buds and fowers in geraniums, azaleas, and rhododendrons. It was most effective as a soil treatment for potted ornamentals. In addition, treatment of stock plants enhances the uniformity of cuttings taken from them. Formulation types GR; SL . PRODUCTS: Discontinued products ‘Phosfeur’* (Perifeur); ‘Phosfon’* (Mobil). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 210 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 750 mg/kg. Tech. product and formulations are irritating to eyes and skin. Toxicity Class WHO (a.i.) II EPA (formulation) II EC Classifcation T; R25| Xn; R21| Xi; R36/38 ECOTOXICOLOGY: Fish LC 50 (96 h) for rainbow trout 115 mg/l. Bees Not hazardous to bees. ENVIRONMENTAL FATE: Soil/Environment DT 50 of chlorphonium in standard German soil 2.2 & 2.3 >28 months, when stored under BBA conditions. Details PM11, Entry 135. chlorphoxim Insecticide IRAC 1B NOMENCLATURE: Common name chlorphoxime ((f) F-ISO); chlorphoxim (BSI, E-ISO) IUPAC name 2-(2-chlorophenyl)-2-(diethoxyphosphinothioyloxyimino)acetonitrile; O,O- diethyl 2-chloro-α-cyanobenzylideneamino-oxyphosphonothioate Chemical Abstracts name 7-(2-chlorophenyl)-4-ethoxy-3,5-dioxa-6-aza-4-phosphaoct- 6-ene-8-nitrile 4-sulfde; formerly 2-chloro-α-[(diethoxyphosphinothioyloxy)imino] benzeneacetonitrile CAS RN [14816–20–7] Development codes BAY SRA 7747; Supplementary Entries – Extended chlorprazophos 123 Bayer 78182 Smiles code CCOP(=S)(OCC)ON=C(C#N)c1ccccc1Cl PHYSICAL CHEMISTRY: Mol. wt. 332.7 M.f. C 12 H 14 ClN 2 O 3 PS Form Colourless solid. M.p. 66.5 °C B.p. Not distillable V.p. <1 mPa (20 °C) Henry <1.96 × 10 –1 Pa m 3 mol –1 (calc.) Solubility In water 1.7 mg/kg (20 °C). In cyclohexane, toluene 400–600 g/kg (20 °C). COMMERCIALISATION: History Insecticide reported by J. E. Hudson & W. O. Obudho (Mosq. News, 1972, 32, 37). Introduced by Bayer AG. Patents DE 1238902 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Insecticide with contact action, and long residual activity. Uses For control of mosquitoes and Simulium fies. Formulation types UL; WP. PRODUCTS: Discontinued products ‘Baythion C’* (Bayer). ANALYSIS: Product analysis by hplc (CIPAC Handbook, 1988, D, 42). Residues determined by glc (D. B. Leuck & M. C. Bowman, J. Econ. Entomol., 1973, 66, 798). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: PDS 32 (1978). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >2500 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >500 mg/kg. NOEL In 90 d feeding trials, mice showed no effect at 50 mg/kg diet. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Low toxicity to birds. Fish LC 50 (96 h) for rainbow trout 0.1–1.0 mg/l; (48 h) for carp 8.5 mg/l. Details PM8, Entry 03010. chlorprazophos Insecticide IRAC 1B NOMENCLATURE: Common name chlorprazophos (BSI, E-ISO, (m) F-ISO) IUPAC name O-(3-chloro-7-methylpyrazolo[1,5-a]pyrimidin-2-yl) O,O-diethyl phosphorothioate (I) Chemical Abstracts name (I) CAS RN [36145–08–1] Development codes HOX 2709 Smiles code CCOP(=S)(OCC)Oc1nn2c(C)ccnc2c1Cl PHYSICAL CHEMISTRY: Mol. wt. 335.8 M.f. C 11 H 15 ClN 3 O 3 PS 124 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorquinox COMMERCIALISATION: History Insecticide evaluated by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. chlorprocarb Herbicide NOMENCLATURE: Common name chlorprocarb (BSI, E-ISO); chlorprocarbe ((m) F-ISO) IUPAC name methyl 3-[1-(chloromethyl)propylcarbamoyloxy]carbanilate Chemical Abstracts name 3-[(methoxycarbonyl)amino]phenyl [1-(chloromethyl) propyl]carbamate; methyl m-hydroxycarbanilate [1-(chloromethyl)propyl] carbamate ester CAS RN [23121–99–5] Development codes BAS 379H (BASF) Smiles code CCC(CCl)NC(=O)Oc1cccc(NC(=O)OC)c1 PHYSICAL CHEMISTRY: Mol. wt. 300.7 M.f. C 13 H 17 ClN 2 O 4 COMMERCIALISATION: History Herbicide introduced by BASF AG. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. chlorquinox Fungicide NOMENCLATURE: Common name chlorquinox (BSI, E-ISO, (m) F-ISO) IUPAC name 5,6,7,8-tetrachloroquinoxaline (I) Chemical Abstracts name (I) CAS RN [3495–42–9] Smiles code Clc1c(Cl)c(Cl)c2nccnc2c1Cl PHYSICAL CHEMISTRY: Mol. wt. 267.9 M.f. C 8 H 2 Cl 4 N 2 COMMERCIALISATION: History Fungicide introduced by Fisons Ltd (later Schering Agrochemicals Ltd). PRODUCTS: Discontinued products ‘Lucel’* (Schering). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Details PM5, p. 119. Supplementary Entries – Extended chlorthiamid 125 chlorthiamid Herbicide HRAC L WSSA 20; benzonitrile NOMENCLATURE: Common name DCBN (JMAF); chlorthiamid (BSI, E-ISO); chlortiamide ((f) F-ISO) IUPAC name 2,6-dichlorothiobenzamide Chemical Abstracts name 2,6-dichlorobenzenecarbothioamide CAS RN [1918–13–4] EC no 217–637–7 Development codes WL 5792 (Shell) Smiles code NC(=S)c1c(Cl)cccc1Cl PHYSICAL CHEMISTRY: Mol. wt. 206.1 M.f. C 7 H 5 Cl 2 NS Form Off-white solid. M.p. 151–152 °C V.p. 0.13 mPa (20 °C) K ow logP = 1.77 Henry 2.82 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.59 (20 °C) Solubility In water 950 mg/l (21 °C). In aromatic and chlorinated hydrocarbons 50–100 g/kg. Stability Thermally stable up to 90 °C. Stable in acidic solutions, but is converted to dichlobenil in alkaline solutions. COMMERCIALISATION: History Herbicide reported by H. Stanford (Proc. Br. Weed Control Conf., 7th, 1964, p. 208). Introduced by Shell Research Ltd. Discontinued by Hodogaya (2012). Patents GB 987253 Manufacturers Hodogaya APPLICATIONS: Biochemistry Precursor of dichlobenil. Mode of action Systemic herbicide, absorbed by the roots and, to some extent, by the leaves, with translocation principally acropetally. Inhibits germination of seeds. Uses Selective control of germinating weeds in pome fruit, currants, gooseberries, raspberries, citrus fruit, vines, olives, lavender, and ornamental plants and shrubs. Control of bracken, grass and broad-leaved weeds in forestry; and docks in meadows and pastures. Total weed control on non-crop land, paths, industrial areas, etc. Formulation types GR . Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Prefx’* (Shell). ANALYSIS: Product by potentiometric titration with silver nitrate (CIPAC Handbook, 1980, 1A, 1158). Residues by glc with ECD (K. I. Beynon et al., J. Sci. Food Agric., 1966, 17, 151–155). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.852 (1996). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. C Cl Cl S NH 2 126 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlorthiophos MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >2000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg. NOEL (90 d) for rats 100 mg/kg diet. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R22 ECOTOXICOLOGY: Birds Acute oral LD 50 for duck 374 mg/kg. Fish LC 50 (96 h) for carp 42 mg/l. Daphnia LC 50 (48 h) 56 mg/l. Algae EC 50 (48 h) 17 mg/l. Bees LD 50 (oral, 48 h) 77.3 μg/bee, LD 50 (contact, 96 h) >100 μg/bee. ENVIRONMENTAL FATE: Animals In rats, following oral administration, there is rapid metabolism and 70% elimination in the urine within 24 h. Soil/Environment In soil, chlorthiamid is converted to dichlobenil (q.v.), which then gradually undergoes microbial degradation to 2,6-dichlorobenzamide and 2,6-dichlorobenzoic acid. Converted to dichlobenil in soil; DT 50 for chlorthiamid + dichlobenilc. 35 d under dry and 14 d under wet conditions. Duration of residual activity in soil isc. 5–7 months. The fate in crops, soils and animals has been reviewed (K. I. Beynon & A. N. Wright, Residue Rev., 1972, 43, 23). Details PM15, Entry 161. chlorthiophos Insecticide IRAC 1B NOMENCLATURE: Common name chlorthiophos (BSI, E-ISO, (m) F-ISO, ANSI, ESA, for an isomeric reaction mixture) IUPAC name O-2,5-dichloro-4-methylthiophenyl O,O-diethyl phosphorothioate (i, main component); O-4,5-dichloro-2-methylthiophenyl O,O-diethyl phosphorothioate (ii, small quantities); O-2,4-dichloro-5-methylthiophenyl O,O-diethyl phosphorothioate (iii, minor component) Chemical Abstracts name O-[2,5-dichloro-4-(methylthio)phenyl] O,O-diethyl phosphorothioate (i); O-[4,5-dichloro-2-(methylthio)phenyl] O,O-diethyl phosphorothioate (ii); O-[2,4-dichloro-5-(methylthio)phenyl] O,O-diethyl phosphorothioate (iii) CAS RN [60238–56–4] mixed isomers; [21923–23–9] isomer (i) EC no 244–663–6 for isomer (i) Development codes S 2957 (Boehringer, Cela GmbH) Smiles code CCOP(=S)(OCC)Oc1cc(Cl)c(SC)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 361.2 M.f. C 11 H 15 Cl 2 O 3 PS 2 Form Yellow-brown liquid. M.p. Crystallises <25 °C B.p. 153–158 °C /0.013 mmHg V.p. 0.53 mPa (25 °C) S.g./ density 1.345 (20 °C) Solubility In water c. 0.3 mg/l (20 °C). Miscible with all common organic solvents. Stability DT 50 42 d (pH <9). COMMERCIALISATION: History Insecticide reported by H. Holtmann & E. Raddatz (Proc. Br. Insectic. Fungic. Conf., Supplementary Entries – Extended chlozolinate 127 6th, 1971, 2, 485). Introduced by C. H. Boehringer Sohn/Cela GmbH (later Shell Agrar GmbH). Patents DE 1298990; GB 1210826 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact and ingested insecticide and acaricide. Uses Effective against Diptera, Hemiptera, Lepidoptera and with some acaricidal activity. Rates 300–1500 g/ha depend on pests and the crop. Formulation types DP; EC; GR; WP. PRODUCTS: Discontinued products ‘Celathion’* (Shell Agrar). ANALYSIS: Product analysis is by bromometric titration. Residues may be determined by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 10.7, female rats 7.8, mice 91.4 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats 153, female rats 121, rabbits 50–58 mg/kg. NOEL (2 y), based on erythrocyte cholinesterase inhibition, for rats 1.6 mg/ kg diet; (1 y) for dogs 1 mg/kg diet. Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R28| T; R24| N; R50, R53| concn. dep. (for isomer (i)) ECOTOXICOLOGY: Birds LC 50 (8 d) for bobwhite quail 213, mallard ducks 0.198 mg/kg diet. Fish LC 50 (96 h) for bluegill 1.3, rainbow trout 0.019 mg/l. Details PM7, Entry 03110. chlozolinate Fungicide FRAC 2, E3; dicarboximide NOMENCLATURE: Common name chlozolinate (BSI, E-ISO, (m) F-ISO) IUPAC name ethyl (±)-3-(3,5-dichlorophenyl)-5-methyl-2,4-dioxo-oxazolidine-5-carboxylate Chemical Abstracts name (±)-ethyl 3-(3,5-dichlorophenyl)-5-methyl-2,4-dioxo- 5-oxazolidinecarboxylate CAS RN [84332–86–5] racemate; [72391–46–9] unstated stereochemistry EC no 282–714–4 Development codes M 8164 (Agrimont) Smiles code CCOC(=O)C1(C)OC(=O)N(C1=O)c2cc(Cl)cc(Cl)c2 Cl Cl O O N O CH 3 CO 2 CH 2 CH 3 128 The Pesticide Manual Sixteenth Edition © BCPC 2012 chlozolinate PHYSICAL CHEMISTRY: Mol. wt. 332.1 M.f. C 13 H 11 Cl 2 NO 5 Form Colourless, almost odourless solid. M.p. 112.6 °C V.p. 0.013 mPa (25 °C, gas saturation method) K ow logP = 3.15 (22 °C) Henry 2.29 × 10 –3 Pa m 3 mol –1 (25 °C, calc.) S.g./density 1.441 (20 °C) Solubility In water c. 2 ppm (25 °C). In acetone, ethyl acetate and 1,2-dichloroethane >250, ethanol c. 13, n-heptanec. 2, xylenec. 60 (all in g/kg, 22 °C). Stability Stable to 250 °C (under nitrogen). Stable to light. In solution, hydrolysis occurs at pH 5–9. COMMERCIALISATION: History Fungicide reported by Di Toro et al. (Atti Giornate Fitopatol., Siusi, 1980). Introduced by Agrimont (later Isagro S.p.A.). Patents BE 874406; DE 2906574; IT 20579/78 Manufacturers Isagro APPLICATIONS: Biochemistry Affects mitogen-activated protein histidine kinase, in osmotic signal transduction. Mode of action Contact fungicide with protective and curative action. Uses Control of Botrytis spp., sclerotinia spp., and monilia spp. in ornamentals, vegetables, vines, pome fruit, stone fruit, sunfowers and strawberries. Can be applied, at 750–1000 g/ha, as a foliar spray or as a soil drench. Formulation types SC. WP. PRODUCTS: Discontinued products ‘Manderol’* (Isagro); ‘Serinal’* (Isagro). ANALYSIS: Product and residues can be determined by glc. Details are available from Isagro. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Rev. Rep. 8397/VI/98 (1999). EU Status (1107/2009) Not approved, 2000/626/EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >4500, mice >10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Non-irritating to skin and eyes (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 (4 h) for rats >10 mg/l air. NOEL (90 d) for rats 200 mg/kg diet; (1 y) for dogs 200 mg/kg diet. ADI/RfD (ECCO) 0.1 mg/kg b.w. [1999]. Other Not mutagenic, not teratogenic. Toxicity Class WHO (a.i.) U EPA (formulation) III EC Classifcation R40| N; R51, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for quail and mallard ducks >4500 mg/kg. Fish LC 50 (96 h) for trout 27.5 mg/l. Daphnia LC 50 (48 h) 1.18 mg/l. Algae EC 50 (96 h) for Selenastrum capricornutum 30 mg/l. Bees LD 50 (oral) >100 μg/bee. Other benefcial Harmless to Phytoseiulus persimilis at up to 2 × recommended application rate. ENVIRONMENTAL FATE: Animals Chlozolinate is readily absorbed, metabolised and excreted. Metabolites identifed in urine of rats are: 3-(3,5-dichlorophenyl)-5-methyloxazolidin-2,4-dione, N-(3,5-dichlorophenyl)-2-hydroxypropionamide, O-1-carboxyethyl-N-3,5-dichlorophenyl carbamate, and N-(3,5-dichloro-2(or 4)-hydroxyphenyl)-2-hydroxypropionamide and its sulfate and glucuronide conjugates. Plants In plants, chlozolinate undergoes hydrolysis and decarboxylation processes, giving the same metabolites as those identifed in animals. Supplementary Entries – Extended cispermethrin 129 Soil/Environment In silt-loam, sandy loam and clay loam soils, hydrolysis and decarboxylation occur; aerobic DT 50 <7 h. Details PM13, Entry 149. ciobutide Plant growth regulator NOMENCLATURE: Common name ciobutide (BSI, E-ISO, (m) F-ISO) IUPAC name (RS)-2-cyano-2-phenylbutyramide Chemical Abstracts name (±)-α-cyano-α-ethylbenzeneacetamide CAS RN [80544–75–8] Smiles code CCC(C#N)(C(=O)N)c1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 188.2 M.f. C 11 H 12 N 2 O COMMERCIALISATION: History Plant growth regulator discovered by EGYT Pharmacochemical Works. cispermethrin Insecticide An isomer pair, component of permethrin. NOMENCLATURE: IUPAC name 3-phenoxybenzyl (1RS)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclo propanecarboxylate; 3-phenoxybenzyl (1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropanecarboxylate Chemical Abstracts name rel-(1R,3R)-(3-phenoxyphenyl)methyl 3-(2,2-dichloro ethenyl)-2,2-dimethylcyclopropanecarboxylate; cis-(±)-(3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate CAS RN [61949–76–6], formerly [52341–33–0]; [54774–45–7] (1R)-cis- resolved isomer; [54774–46–8] (1S)- cis- isomer Development codes FMC 35171; NRDC 148; NRDC 167 (for the (1R)-cis- resolved isomer) PHYSICAL CHEMISTRY: Mol. wt. 391.3 M.f. C 21 H 20 Cl 2 O 3 ANALYSIS: Analysis of pyrethroids reviewed by E. Papadopoulou-Mourkidou in Comp. Anal. Profles. Permethrin isomers in drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: See A. J. Gray & D. M. Soderlund, Chapt. 5 in Insecticides. O CH 2 C CH CH 3 CH 3 Cl C O O Cl 130 The Pesticide Manual Sixteenth Edition © BCPC 2012 CL900167 CL 304,415 Herbicide safener NOMENCLATURE: IUPAC name 4-carboxymethylchroman-4-carboxylic acid Chemical Abstracts name 4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid CAS RN [31541–57–8], formely [217311–61–0] Development codes CL 304,415 Smiles code OC(=O)CC1(CCOc2ccccc21)C(=O)O PHYSICAL CHEMISTRY: Mol. wt. 236.2 M.f. C 12 H 12 O 5 COMMERCIALISATION: History Herbicide safener, reported by G. E. Cary et al. (Proc. 8th IUPAC International Congress of Pesticide Chemistry, Washington, 1994). Developed by American Cyanamid Co. APPLICATIONS: Biochemistry Increases the rate of metabolism of imazethapyr in maize. Uses Safens maize against injury by imazethapyr and other imidazolinone herbicides. Details PM10, Entry 146. CL900167 Acaricide NOMENCLATURE: Chemical Abstracts name 4-[(4-chloro-α,α,α-trifuoro-m-tolyl)oxy]-6-[(α,α,α,4- tetrafuoro-m-tolyl)oxy]-pyrimidine Development codes CL 900,167 (Shell); AC 9 00,167 (Cyanamid) PHYSICAL CHEMISTRY: Mol. wt. 452.7 M.f. C 18 H 8 ClF 7 N 2 O 2 M.p. –65 °C V.p.c. 1 × 10 –1 mPa S.g./density 1.033 (20 °C) Solubility In water <0.1 ppm. O HO 2 C CH 2 CO 2 H N N O F F F F O F F F Cl Supplementary Entries – Extended cliodinate 131 climbazole Fungicide NOMENCLATURE: Common name climbazole (BAN) IUPAC name 1-(4-chlorophenoxy)-1-(imidazol-1-yl)-3,3-dimethylbutanone Chemical Abstracts name 1-(4-chlorophenoxy)-1-(1H-imidazol-1-yl)-3,3- dimethyl-2-butanone CAS RN [38083–17–9] Development codes BAY MEB 6401 Smiles code CC(C)(C)C(=O)C(Oc1ccc(Cl)cc1)n2ccnc2 PHYSICAL CHEMISTRY: Mol. wt. 292.8 M.f. C 15 H 17 ClN 2 O 2 Form Colourless crystalline solid. M.p. 95.5 °C V.p. 1.0 mPa (extrapolated to 50 °C) Solubility In water 5.5 mg/l (20 °C). In cyclohexanone 400–600, isopropanol 100–200 g/kg (20 °C). COMMERCIALISATION: History Fungicide introduced by Bayer AG. Patents BE 2600800 APPLICATIONS: Biochemistry Sterol demethylation inhibitor. Uses A fungicide, effective against Aspergillus, Candida, Paecilomyces and Penicillium spp. on various household materials, utensils and parts of buildings. PRODUCTS: Discontinued products ‘Baysan’* (Bayer). ANALYSIS: Product analysis is by glc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 400 mg/kg. Details PM7, Entry 02760. cliodinate Herbicide NOMENCLATURE: Common name cliodinate (BSI, E-ISO, (m) F-ISO) IUPAC name 2-chloro-3,5-di-iodo-4-pyridyl acetate Chemical Abstracts name 2-chloro-3,5-di-iodo-4-pyridinyl acetate CAS RN [69148–12–5] Development codes ASD 2288 Smiles code CC(=O)Oc1c(I)cnc(Cl)c1I PHYSICAL CHEMISTRY: Mol. wt. 423.4 M.f. C 7 H 4 ClI 2 NO 2 COMMERCIALISATION: History Herbicide evaluated by Celamerck GmbH KG (later Shell Agrar GmbH). 132 The Pesticide Manual Sixteenth Edition © BCPC 2012 cloethocarb cloethocarb Insecticide, nematicide IRAC 1A NOMENCLATURE: Common name cloé(thocarb) ((m) F-ISO); cloethocarb (BSI, E-ISO) IUPAC name 2-(2-chloro-1-methoxyethoxy)phenyl methylcarbamate Chemical Abstracts name 2-(2-chloro-1-methoxyethoxy)phenyl methylcarbamate CAS RN [51487–69–5] Development codes BAS 263I (BASF) Smiles code CNC(=O)Oc1ccccc1OC(CCl)OC PHYSICAL CHEMISTRY: Mol. wt. 259.7 M.f. C 11 H 14 ClNO 4 Form Colourless crystals. M.p. 80 °C; (tech.: 69–75 °C) V.p. 0.01 mPa (20 °C) Henry 2.00 × 10 –6 Pa m 3 mol –1 (calc.) Solubility In water 1.3 g/kg (20 °C). In acetone, chloroform >1000, ethanol 153 (all in g/kg, 20 °C). Stability Non-hygroscopic. Hydrolysed by strong acids or alkalis. COMMERCIALISATION: History Insecticide reported by V. Harries et al. (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1978, 45, 739). Introduced by BASF AG. Patents DE 2231249; GB 1426233; US 3962316 Manufacturers BASF APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and nematicide with contact and stomach action. Absorbed by the roots and translocated to the foliage. Uses Control of corn rootworms on maize; colorado beetle on potatoes; and a variety of aphids, caterpillars, scales, nematodes etc. on peanuts, potatoes, rice, sugar cane, tobacco, sorghum, coffee, wheat, oilseed rape and alfalfa. Could be applied as a granular soil treatment, as a seed treatment, or as bait pellets. Formulation types GR; FS; BR . PRODUCTS: Discontinued products ‘Lance’* (BASF). ANALYSIS: Product analysis by hplc. Residues determined by alkaline hydrolysis to a derivative which is determined by hplc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 35.4, mice 70.4 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 4000 mg/kg. NOEL (1 y) for dogs 0.5 mg/kg daily (capsule administration); OCONHCH 3 OCHCH 2 Cl OCH 3 Supplementary Entries – Extended clofencet-potassium; clofencet 133 for rats 25 mg/kg diet (c. 1 mg/kg daily); for mice 10 mg/kg diet (c. 1 mg/kg daily). Toxicity Class WHO (a.i.) Ib EPA (formulation) II ECOTOXICOLOGY: Fish Moderately toxic to fsh. Bees Toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Residual activity is 3–7 weeks. Details PM10, Entry 149. clofencet-potassium; clofencet Plant growth regulator NOMENCLATURE: Common name clofencet (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name potassium 2-(4-chlorophenyl)-3-ethyl-2,5-dihydro-5-oxopyridazine-4- carboxylate Chemical Abstracts name potassium 2-(4-chlorophenyl)-3-ethyl-2,5-dihydro-5-oxo- 4-pyridazinecarboxylate CAS RN [82697–71–0] clofencet-potassium; [129025–54–3] clofencet Development codes MON 21233 (Monsanto); RH 754 (Rohm & Haas); RH0754 (Rohm & Haas); FC 4001 (Zeneca); ICIS 0754 (ICI) (all clofencet-potassium); MON 21200 (Monsanto) (clofencet) Smiles code CCc1c(C(=O)O)c(=O)cnn1c2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 316.8; 278.7 (clofencet) M.f. C 13 H 10 ClKN 2 O 3 ; clofencet C 13 H 11 ClN 2 O 3 M.p. 269 °C (decomp.) V.p. <1 × 10 –2 mPa (25 °C) K ow logP = –2.2 (25 °C) Henry <5.7 × 10-9 Pa m 3 mol –1 (25 °C, calc.) S.g./density 1.44 (20 °C) Solubility In water >552; >655 (pH 5), >696 (pH 7), >658 (pH 9) (all in g/l, 23 °C). In methanol 16, acetone <0.5, dichloromethane <0.4, toluene <0.4, ethyl acetate <0.5, n-hexane <0.6 (all in g/l, 24 °C). Stability Stable 14 d (54 °C). Stable to hydrolysis in sterile aqueous pH 5, 7, and 9 buffered solutions. Moderately persistent to aqueous photolysis; DT 50 increases with pH. pKa 2.83 (20 °C) (clofencet) COMMERCIALISATION: History Discovered by Rohm & Haas Co. (later Dow AgroSciences). Introduced by Monsanto Co. for use in wheat in 1997. APPLICATIONS: Mode of action Systemic. Inhibits pollen formation. Uses The potassium salt is a chemical hybridising agent for wheat. Applied at 3–5 kg/ha. Formulation types SC. PRODUCTS: Discontinued products ‘Detasselor’* (potassium salt) (Monsanto); ‘Genesis’* (potassium salt) (Monsanto). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EPA Fact Sheet, Feb. 1997. EU Status (1107/2009) Not approved, 2004/129/EC. 134 The Pesticide Manual Sixteenth Edition © BCPC 2012 clofop; clofop-isobutyl MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 3437, female rats 3150 mg/kg. Skin and eye Acute dermal LD 50 for rats >5000 mg/kg. Eye irritant; not a skin irritant (rabbits). Not a skin sensitiser (guinea pigs). Inhalation EC 50 for rats >3.8 mg/l. NOEL (1 y) for dogs 5.0 mg/kg daily. ADI/RfD (EPA) cRfD 0.05 mg/kg b.w. [1997] ECOTOXICOLOGY: Birds Acute oral LD 50 for ducks >2000, quail 1414 mg/kg. Dietary LC 50 for ducks and quail >4818 ppm. Fish LC 50 for bluegill sunfsh >1070, rainbow trout >990 ppb. Daphnia EC 50 >1193 mg/l. Algae EbC50 (96 h) for Selenastrum capricornutum 141 mg/l; ErC50 374 mg/l. Other aquatic spp. IC50 (14 d) for Lemna gibba (G3) >6.1 mg/l. Bees LD 50 (48 h) (contact and oral) >100 μg/bee. Worms EC 50 >1000 ppm. ENVIRONMENTAL FATE: Animals In rats, clofencet was rapidly absorbed and excreted; >78% of the administered 14 C-label was eliminated in the urine within 24 h. Clofencet was eliminated mostly unmetabolised and mainly in the urine. At 7 days post-dosing, <1% was retained in the tissue. Plants Clofencet is poorly metabolised in wheat, >80% of the residue in wheat seed, andc. 70% of the residue in wheat straw is unmetabolised clofencet. Soil/Environment Metabolism of clofencet in laboratory soil studies is very slow. After one year in loamy sand (pH 6.0, 4.5% o.m.) and silt loam (pH 7.7, 2.4% o.m.),c. 70% of the applied clofencet remains; the main route of dissipation is soil binding. Clofencet is fairly stable to soil photolysis (74–81% of parent clofencet remains after 30–32 d). DT 50 20–28 d in aqueous solutions (pH 5, 7 and 9). In European feld dissipation studies, DT 50 in silty clay and silty clay loam soils (pH 6.6–7.8) 25–66 d for three sites, although slower degradation was seen at some sites. Batch equilibrium studies and pKa considerations suggest that clofencet is very mobile in sand, loamy sand, and silt loam soils, but laboratory and feld studies suggest that the signifcant soil binding which occurs with time mitigates the tendency towards mobility. Clofencet has the potential for runoff or soil mobility but, in practice, because of specialised use and stewardship practices, effects of mobility and persistence are less likely to be signifcant. Details PM13, Entry 157. clofop; clofop-isobutyl Herbicide NOMENCLATURE: Common name clofop (BSI, E-ISO, (m) F-ISO, WSSA) IUPAC name (±)-2-[4-(4-chlorophenoxy)phenoxy]propionic acid Chemical Abstracts name (±)-2-[4-(4-chlorophenoxy)phenoxy]propanoic acid CAS RN [59621–49–7] racemic clofop; [26129–32–8] clofop (unstated stereochemistry); [51337–71–4] clofop-isobutyl (unstated stereochemistry) Development codes Hoe 22 870 Supplementary Entries – Extended cloproxydim 135 PHYSICAL CHEMISTRY: Mol. wt. 292.7; (isobutyl ester 348.8) M.f. C 15 H 13 ClO 4 ; (isobutyl ester C 19 H 21 ClO 4 ) Form The ester is a colourless crystalline solid. M.p. 39–40 °C Solubility In water 180 mg/l (22 °C). Highly soluble in acetone and xylene. COMMERCIALISATION: History Herbicide described by F. Schwerdtle et al. (Mitt. Biol. Bundesanst. Land-Forstwirtsch. Berlin-Dahlem, 1975, 165, 171). Clofop-isobutyl introduced by Hoechst AG. APPLICATIONS: Mode of action Taken up through the leaves and roots and is selective in nearly all cultivated dicotyledonous crops as well as in cereals. Details PM6, p. 125. Uses Clofop- isobutyl is a post-emergence herbicide efffective against annual grasses such as Alopecurus myosuroides, Echinochloa crus-galli, Eleusine, Panicum and Setaria spp. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 1208 mg/kg. NOEL (90 d) for dogs and male rats 32 mg/kg diet. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22 (clofop-isobutyl) Details PM6, p. 125. cloproxydim Herbicide NOMENCLATURE: Common name clopropoxydim* (former WSSA); cloproxydim (BSI, ANSI, WSSA, E-ISO); cloproxydime ((f) F-ISO) IUPAC name (±)-2-[1-(3-chloroallyloxy)iminobutyl]-5-(2-ethylthiopropyl)-3- hydroxycyclohex-2-enone Chemical Abstracts name 2-[1-[[(3-chloro-2-propenyl)oxy]imino]butyl]-5- [2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one CAS RN [95480–33–4] Development codes RE-36 290 Smiles code CCCC(=NOCC=CCl)C1=C(O)CC(CC(C)SCC)CC1=O PHYSICAL CHEMISTRY: Mol. wt. 373.9 M.f. C 18 H 28 ClNO 3 S Form Liquid. V.p. <0.013 mPa (20 °C) S.g./density 1.15 (20 °C) Solubility Soluble in most organic solvents. Stability Unstable in acid or alkaline solution, or on heating. COMMERCIALISATION: History Herbicide evaluated by Chevron Chemical Company LLC. APPLICATIONS: Mode of action Selective herbicide. Uses A post-em. herbicide controlling a wide range of annual and perennial grasses in beans, cotton, potatoes, sugar beet, and most vegetable crops. Formulation types EC. 136 The Pesticide Manual Sixteenth Edition © BCPC 2012 coumafuryl PRODUCTS: Discontinued products ‘Selectone’* (Chevron). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >500 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats >500 mg/kg. Other Non-mutagenic in the Ames assay. copper bis(3-phenylsalicylate) Fungicide NOMENCLATURE: IUPAC name copper bis(3-phenylsalicylate) Chemical Abstracts name bis(2-hydroxy[1,1′-biphenyl]-3-carboxylato-O 2 ,O 0 )copper CAS RN [5328–04–1] Smiles code [Cu+2].Oc1c(cccc1c2ccccc2)C(=O)[O-]. Oc1c(cccc1c2ccccc2)C(=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 490.0 M.f. C 26 H 18 CuO 6 COMMERCIALISATION: History Fungicide. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 200 (1998) is a general review of copper and copper compounds. copper zinc chromate Fungicide NOMENCLATURE: IUPAC name copper zinc chromate (indefnite composition) Development codes Crag Fungicide 658; Experimental Fungicide 658 COMMERCIALISATION: History Fungicide evaluated by Union Carbide Corp. (later Rhône-Poulenc Agrochimie). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 200 (1998) is a general review of copper and copper compounds. coumafuryl Rodenticide NOMENCLATURE: Common name coumafuryl (BSI since 1984, E-ISO, (m) F-ISO); fumarin (BSI pre-1984, Canada); tomarin* (Turkey pre-1984) IUPAC name 3-[1-(2-furyl)-3-oxobutyl]-4-hydroxycoumarin Supplementary Entries – Extended coumithoate 137 Chemical Abstracts name 3-[1-(2-furanyl)-3-oxobutyl]-4-hydroxy-2H-1- benzopyran-2-one CAS RN [117–52–2] unstated stereochemistry EC no 204–195–5 Smiles code CC(=O)CC(c1ccco1)c2c(O)c3ccccc3oc2=O PHYSICAL CHEMISTRY: Mol. wt. 298.3 M.f. C 17 H 14 O 5 COMMERCIALISATION: History Rodenticide developed by Amchem Chemical Co. (later Rhône-Poulenc Agrochimie). APPLICATIONS: Mode of action Anticoagulant rodenticide. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 175 (1995). EU Status (1107/2009) Not approved, 2004/129/EC. MAMMALIAN TOXICOLOGY: EC Classifcation T; R25, R48/25| R52, R53 coumithoate Insecticide IRAC 1B NOMENCLATURE: Common name coumithoate (BSI, E-ISO, (m) F-ISO) IUPAC name O,O-diethyl O-(7,8,9,10-tetrahydro-6-oxo-6H-benzo[c]chromen-3-yl) phosphorothioate; 3-diethoxyphosphinothioyloxy-7,8,9,10-tetrahydrobenzo[c]chromen-6-one Chemical Abstracts name O,O-diethyl O-(7,8,9,10-tetrahydro-6-oxo-6H-dibenzo[b,d] pyran-3-yl) phosphorothioate CAS RN [572–48–5] Smiles code CCOP(=S)(OCC)Oc1ccc2c3CCCCc3c(=O)oc2c1 PHYSICAL CHEMISTRY: Mol. wt. 368.4 M.f. C 17 H 21 O 5 PS COMMERCIALISATION: History Insecticide introduced by Montecatini S.p.A. (later Agrimont S.p.A.). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Dithion’* (Agrimont); ‘Dition’* (Agrimont). MAMMALIAN TOXICOLOGY: EC Classifcation T; R25 138 The Pesticide Manual Sixteenth Edition © BCPC 2012 credazine CP 17029 Herbicide NOMENCLATURE: IUPAC name N 2 ,N4-bis(3-methoxypropyl)-6-methylthio-1,3,5-triazine-2,4-diamine; 2,4-bis(3-methoxypropylamino)-6-(methylthio)-1,3,5-triazine Chemical Abstracts name N,N′-bis(3-methoxypropyl)-6-(methylthio)-1,3,5-triazine-2,4- diamine Other names MPMT CAS RN [845–52–3] Development codes CP 17 029 Smiles code COCCCNc1nc(NCCCOC)nc(SC)n1 PHYSICAL CHEMISTRY: Mol. wt. 301.4 M.f. C 12 H 23 N 5 O 2 S COMMERCIALISATION: History Herbicide introduced by Monsanto Co. PRODUCTS: Discontinued products ‘Lambast’* (Monsanto). credazine Herbicide NOMENCLATURE: Common name credazine (JMAF) IUPAC name pyridazin-3-yl o-tolyl ether Chemical Abstracts name 3-(2-methylphenoxy)pyridazine CAS RN [14491– 59–9] Development codes H 722; SW-6701; SW-6721 (all Sankyo) Smiles code Cc1ccccc1Oc2cccnn2 PHYSICAL CHEMISTRY: Mol. wt. 186.2 M.f. C 11 H 10 N 2 O Form Colourless needles. M.p. 78 °C Solubility In water 2 g/l (room temperature). Readily soluble in organic solvents. Stability Stable to light, heat and humidity. COMMERCIALISATION: History Herbicide reported by T. Jojima et al. (Agric. Biol. Chem., 1968, 32, 1376; 1969, 33, 96). Introduced by Sankyo Co. Ltd. Patents JP 509596. APPLICATIONS: Mode of action Selective herbicide. Uses Selective soil herbicide, used in Japan for the control of annual grasses and some broad-leaved weeds in tomatoes, pimentoes and strawberries, at 2–3 kg ha. PRODUCTS: Discontinued products ‘Kusakira’* (Sankyo). ANALYSIS: Product analysis by glc. Residues are determined by glc after separation by tlc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3090, mice 569 mg/kg. Toxicity Class WHO (a.i.) U Supplementary Entries – Extended crimidine 139 ENVIRONMENTAL FATE: Plants In plants, the major metabolites are (2H)-pyridazin-3-one and 3-(1-β-D- glucosyloxy)pyridazine (M. Nakagawa et al., Agric. Biol. Chem., 1971, 25, 764). Soil/Environment Moderately persistent in soil (S. Yoshimura et al., Zasso Kenkyu, 1969, No. 7, p. 84). Details PM6, p. 522. crimidine Rodenticide NOMENCLATURE: Common name crimidine (BSI, E-ISO, (f) F-ISO) IUPAC name 2-chloro-N,N,6-trimethylpyrimidin-4-amine Chemical Abstracts name 2-chloro-N,N,6-trimethyl-4-pyrimidinamine CAS RN [535–89–7] EC no 208–622–6 Smiles code CN(C)c1cc(C)nc(Cl)n1 PHYSICAL CHEMISTRY: Composition Tech. containsc. 20% of the non-rodenticidal 4-chloro-N,N,6- trimethylpyrimidin-2-ylamine. Mol. wt. 171.6 M.f. C 7 H 10 ClN 3 Form Tech. is a brownish wax. M.p. 87 °C B.p. 140–147 °C /4 mmHg Solubility In water 9.4 g/l (20 °C). In dichloromethane 600–1200, isopropanol 100–200 (both g/l, 20 °C). COMMERCIALISATION: History Rodenticide introduced in the early 1940s by Bayer AG. Patents US 2219858 APPLICATIONS: Formulation types AB. PRODUCTS: Discontinued products ‘Castrix’* (Bayer). ANALYSIS: Product and residue analysis is by hplc (E. Mõllhoff, Pfanz.-Nachr. Bayer (Engl. Ed.), 1980, 33, 86). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, 2004/129/EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1.25, rabbits 5 mg/kg. Toxicity Class WHO (a.i.) O EC Classifcation T+; R28 ECOTOXICOLOGY: Birds It is not a cumulative poison; birds are not harmed by the ingestion of a few grains of the formulation. Details PM7, Entry 03380. 140 The Pesticide Manual Sixteenth Edition © BCPC 2012 crotoxyphos crotoxyphos Insecticide, ixodicide IRAC 1B NOMENCLATURE: Common name crotoxyphos (BSI, E-ISO, (m) F-ISO, ESA); crotoxyfos (BAN) IUPAC name 1-phenylethyl 3-(dimethoxyphosphinoyloxy)isocrotonate; dimethyl (E)-1- methyl-2-(1-phenylethoxycarbonyl)vinyl phosphate Chemical Abstracts name (E)-1-phenylethyl 3-[(dimethoxyphosphinyl)oxy]-2-butenoate CAS RN [7700–17–6] EC no 231–720–5 Development codes SD 4294 (Shell) Smiles code COP(=O)(OC)OC(=CC(=O)OC(C)c1ccccc1)C PHYSICAL CHEMISTRY: Composition Tech. is 80%. Mol. wt. 314.3 M.f. C 14 H 19 O 6 P Form Tech. is a light straw- coloured liquid. B.p. 135 °C /0.03 mmHg (tech.) V.p. 1.9 mPa (20 °C) Henry 5.97 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.2 (20 °C, tech.) Solubility In water 1 g/l (room temperature). Soluble in acetone, ethanol, isopropanol, xylene. Stability DT 50 87 h (pH 1), 35 h (pH 9) (38 °C) COMMERCIALISATION: History Insecticide reported by C. P. Weidenback & R. L. Younger (J. Econ. Entomol., 1962, 55, 793). Introduced by the Shell Development Co. Patents US 3068268; US 3116201 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses An insecticide with a rapid action and moderately persistent residual effect on a wide range of external insect pests of livestock and was recommended for the control of fies, mites and ticks on cattle and pigs. Formulation types EC. Compatibility Incompatible with most mineral carriers, except synthetic silicas such as ‘Colloidal Silica K320’ and ‘Hisil 233’. PRODUCTS: Discontinued products ‘Ciodrin’* (Shell). ANALYSIS: Product analysis by i.r. spectroscopy or by glc. Residues determined by glc with FPD (P. E. Porter, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1967, 5, 243; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 325). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 52.8, mice 90 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 384 mg/kg. NOEL In 90 d feeding trials, no effect on growth nor histopathological change observed for male rats receiving 900 mg/kg diet, and for female rats receiving 300 mg/kg diet. Toxicity Class WHO (a.i.) Ib EC Classifcation T; R24/25| N; R50, R53| concn. dep. Supplementary Entries – Extended crufomate 141 ENVIRONMENTAL FATE: Metabolism and breakdown in plant, animals and soil has been reviewed (K. I. Beynon et al., Residue Rev., 1973, 47, 55). Details PM8, Entry 03390. crufomate Anthelmintic, insecticide IRAC 1B NOMENCLATURE: Common name crufomate (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name 4-tert-butyl-2-chlorophenyl methyl methylphosphoramidate Chemical Abstracts name 2-chloro-4-(1,1-dimethylethyl)phenyl methyl methylphosphoramidate CAS RN [299–86–5] EC no 206–083–1 Development codes Dowco 132 Smiles code CNP(=O)(OC)Oc1ccc(cc1Cl)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 291.7 M.f. C 12 H 19 ClNO 3 P Form Colourless crystals. M.p. 60 °C Solubility Practically insoluble in water. Readily soluble in acetone, acetonitrile, benzene, carbon tetrachloride; practically insoluble in light petroleum. Stability Stable at pH ≤7.0 but is incompatible with alkaline pesticides and is decomposed in strongly acidic media. COMMERCIALISATION: History Veterinary insecticide and anthelmintic reported by J. F. Landram & R. J. Shaver (J. Parasitol., 1959, 45, 55). Introduced by Dow Chemical Co. (later DowElanco). Patents BE 579237. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide Uses Systemic insecticide and anthelmintic used mainly for the treatment of cattle against Warble fies, ectoparasites and helminths. Compatibility Incompatible with alkaline pesticides. PRODUCTS: Discontinued products ‘Ruelene’* (DowElanco). ANALYSIS: Product analysis is by i.r. spectroscopy, with carbon disulfde as standard. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 11 (1968), 19 (1972). ICSC.143 (1995). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 770–950, rabbits 400–600 mg/kg. ADI/RfD (JMPR) 0.1 mg/kg b.w. [1968]. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R21/22| N; R50, R53 Details PM6, p. 131. 142 The Pesticide Manual Sixteenth Edition © BCPC 2012 cufraneb CS 708 Insecticide NOMENCLATURE: IUPAC name 1,1-bis(4-chlorophenyl)-2-nitrobutane (i) + 1,1-bis(4-chlorophenyl)-2- nitropropane (ii) Chemical Abstracts name 1,1′-(2-nitrobutylidene)bis[4-chlorobenzene] (i) + 1,1′-(2-nitropropylidene)bis[4-chlorobenzene] (ii) CAS RN [117–26–0] (i); [117–27–1] (ii); [8027–00–7] (i) + (ii), formerly [8002–82–2] Development codes CS 674A (i); CS 645A (ii); CS 708 (i + ii) Smiles code CCC(C(c1ccc(Cl)cc1)c2ccc(Cl)cc2)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 324.2 (i); 310.2 (ii) M.f. C 16 H 15 Cl 2 NO 2 (i); C 15 H 13 Cl 2 NO 2 (ii) COMMERCIALISATION: History Insecticide introduced by Commercial Solvents Corp. PRODUCTS: Discontinued products ‘Bulan’* ((i)) (Commercial Solvents); ‘Dilan’* ((i) + (ii)) (Commercial Solvents); ‘Prolan’* (Commercial Solvents). Details PM5, p. 176. cufraneb Acaricide, fungicide NOMENCLATURE: Common name cufraneb (BSI, E-ISO); cufranè(be) ((m) F-ISO) IUPAC name ethylenebis(dithiocarbamate) mixed metal complex containing not less than 8.15% (m/m) of zinc, 8.05% (m/m) of manganese, 5.5% (m/m) of copper and 1.0% (m/m) of iron Chemical Abstracts name cufraneb (not defned in 9CI; see 8CI) CAS RN [11096–18–7] COMMERCIALISATION: History Fungicide introduced by Universal Crop Protection Ltd. APPLICATIONS: Biochemistry Non-specifc thiol reactant, inhibiting respiration. Mode of action Foliar, preventive fungicide with secondary acaricidal activity. Uses Effective against Phytophthora infestans in potatoes and tomatoes, Nectria galligena in pome fruit, Pseudomonas mors- prunorum in cherries, Taphrina deformans in stone fruit and Pseudopeziza ribis in bush fruit. Also controls citrus rust mites. Formulation types WP. PRODUCTS: Discontinued products ‘Cufram Z’* (UCP); Discontinued mixtures ‘Macuprax’* (+ Bordeaux mixture) (Agtrol International). Supplementary Entries – Extended cupric hydrazinium sulfate 143 ANALYSIS: Identifed colorimetrically (CIPAC Handbook, 1994, F, 320). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 78 (1988); a general review of dithiocarbamates and their degradation products. EHC 200 (1998) is a general review of copper and copper compounds. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2700 mg/kg. Skin and eye Irritating to skin, eyes and respiratory system. Toxicity Class EPA (formulation) III ECOTOXICOLOGY: Bees Not toxic to bees. Details PM9, Entry 3420. m-cumenyl methylcarbamate Insecticide NOMENCLATURE: IUPAC name m-cumenyl methylcarbamate; 3-isopropylphenyl methylcarbamate Chemical Abstracts name 3-(1-methylethyl)phenyl methylcarbamate Other names IPMC CAS RN [64–00–6] Development codes AC 5727 (Hercules); UC 10 854 (Union Carbide) Smiles code CNC(=O)Oc1cccc(c1)C(C)C PHYSICAL CHEMISTRY: Mol. wt. 193.2 M.f. C 11 H 15 NO 2 COMMERCIALISATION: History Insecticide introduced by Hercules Inc. (later Nor-Am) and Union Carbide Corp. (later Rhône-Poulenc Agrochimie). APPLICATIONS: Uses For use in rice. cupric hydrazinium sulfate Fungicide NOMENCLATURE: IUPAC name copper(II) dihydrazinium disulfate Chemical Abstracts name bis(hydrazine)bis(hydrogen sulfato)copper Other names cupric hydrazinium sulfate CAS RN [33271–65–7] Development codes Mathieson 466 Smiles code [H+].[H+].N[NH2+][Cu+2][NH2+]N.[O-]S(=O)(=O)[O-].[O-]S(=O)(=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 321.8 M.f. CuH 10 N 4 O 8 S 2 COMMERCIALISATION: History Fungicide introduced by Olin Mathieson Chemical Corp. 144 The Pesticide Manual Sixteenth Edition © BCPC 2012 cuprous chloride PRODUCTS: Discontinued products ‘Omazene’* (Olin). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 200 (1998) is a general review of copper and copper compounds. cuprobam Fungicide NOMENCLATURE: Common name cuprobame ((m) France); cuprobam (BSI) IUPAC name tricopper dichloride dimethyldithiocarbamate Chemical Abstracts name dichloro(dimethylcarbamodithioato)tricopper CAS RN [7076–63–3] PHYSICAL CHEMISTRY: Mol. wt. 381.7 M.f. C 3 H 6 Cl 2 Cu 3 NS 2 COMMERCIALISATION: History Fungicide. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 200 (1998) is a general review of copper and copper compounds. cuprous chloride Plant growth regulator NOMENCLATURE: Chemical Abstracts name copper chloride CAS RN [7758–89–6] PHYSICAL CHEMISTRY: Form Grey tan or green powder. M.p. >430 °C V.p. 1.3 (546 °C) S.g./density 4.14 Solubility In water 0.62 g/100 g. COMMERCIALISATION: History First registered in USA in 1998. APPLICATIONS: Uses Incorporated into plastic plant pots, where it inhibits root growth when seedling roots reach the pot wall; this prevents root circling. PRODUCTS: Other products ‘Migratrol’ (Premium). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 200 (1998) is a general review of copper and copper compounds. EPA Fact Sheet, Sep. 1998. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 50–500 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 200–2000 mg/kg. Eye and skin irritant. Skin sensitiser. Inhalation LC 50 for rats 2–20 mg/l. ADI/RfD (JECFA evaluation) copper compounds 0.5 mg/kg [1982]. Supplementary Entries – Extended cyanofenphos 145 cyanatryn Herbicide NOMENCLATURE: Common name cyanatryn (BSI, E-ISO); cyanatryne ((f) F-ISO) IUPAC name 2-(4-ethylamino-6-methylthio-1,3,5-triazin-2-ylamino)-2- methylpropiononitrile Chemical Abstracts name 2-[[4-(ethylamino)-6-(methylthio)-1,3,5-triazin-2-yl]amino]- 2-methylpropanenitrile CAS RN [21689–84–9] Development codes WL 63 611 Smiles code CCNc1nc(NC(C)(C)C#N)nc(SC)n1 PHYSICAL CHEMISTRY: Mol. wt. 252.3 M.f. C 10 H 16 N 6 S COMMERCIALISATION: History Herbicide reported by V. V. Dovlatyan & F. V. Avetisyan (Arm. Khim. Zh., 1972, 25, 880) and evaluated by Shell Research Ltd. 2-cyano-3-(2,4-dichlorophenyl)acrylic acid Plant growth regulator NOMENCLATURE: IUPAC name 2-cyano-3-(2,4-dichlorophenyl)acrylic acid Chemical Abstracts name 2-cyano-3-(2,4-dichlorophenyl)-2-propenoic acid CAS RN [6013–05–4] Development codes Ethyl 214 Smiles code OC(=O)/C(=C\ c1ccc(Cl)cc1Cl)/C#N;without stereochemistry:OC(=O)C(=Cc1ccc(Cl)cc1Cl)C#N PHYSICAL CHEMISTRY: Mol. wt. 242.1 M.f. C 10 H 5 Cl 2 NO 2 COMMERCIALISATION: History Plant growth regulator developed by Ethyl Corp. Agrochemicals (later Nor-Am). cyanofenphos Insecticide IRAC 1B NOMENCLATURE: Common name CYP (JMAF); cyanofenphos (BSI, E-ISO); cyanophenphos (F-ISO) IUPAC name O-4-cyanophenyl O-ethyl phenylphosphonothioate Chemical Abstracts name O-(4-cyanophenyl) O-ethyl phenylphosphonothioate CAS RN [13067–93–1] Development codes S-4087 (Sumitomo Chemical) Smiles code CCOP(=S)(Oc1ccc(C#N)cc1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 303.3 M.f. C 15 H 14 NO 2 PS Form Tech. is a white or slightly yellowish solid. M.p. 71–78 °C (tech.) V.p. 0.00137 mPa (20 °C) Solubility In water 0.6 mg/l (30 °C). In methanol 89 g/kg (30 °C); in xylene 515 g/kg (27 °C). 146 The Pesticide Manual Sixteenth Edition © BCPC 2012 cyanthoate COMMERCIALISATION: History Insecticide reported by Y. Nishizawa (Bull. Agric. Chem. Soc. Japan, 1960, 24, 744). Introduced by Sumitomo Chemical Co., Ltd. Patents JP 410930; JP 410925; GB 929738 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses An insecticide effective against penetrating and chewing insects, cotton bollworms, gall midges, rice borers and other insects on fruits and vegetables. Formulation types EC. PRODUCTS: Discontinued products ‘Surecide’* (Sumitomo Chemical). ANALYSIS: Product analysis by glc. Residues in milk and meat determined by glc with FPD (J. Miyamoto et al., Nihon Noyaku Gakkaishi, 1977, 2, 1). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Evaln. 39 (1982). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 89 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats >1000, female rats 640 mg/kg. ADI/RfD (JMPR) Temporary ADI withdrawn (1983). Toxicity Class WHO (a.i.) II EC Classifcation T; R25, R39/25| Xn; R21| Xi; R36| N; R51, R53 Details PM7, Entry 03490. cyanthoate Acaricide, insecticide NOMENCLATURE: Common name cyanthoate (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name S-[N-(1-cyano-1-methylethyl)carbamoylmethyl] O,O-diethyl phosphorothioate; N-(1-cyano-1-methylethyl)-2-(diethoxyphosphinoylthio)acetamide Chemical Abstracts name S-[2-[(1-cyano-1-methylethyl)amino]-2-oxoethyl] O,O-diethyl phosphorothioate CAS RN [3734–95–0] EC no 223–099–4 Development codes M 1568 Smiles code CCOP(=O)(OCC)SCC(=O)NC(C)(C)C#N PHYSICAL CHEMISTRY: Mol. wt. 294.3 M.f. C 10 H 19 N 2 O 4 PS COMMERCIALISATION: History Insecticide and acaricide reported by F. Galbaiti (Proc. Br. Insectic. Fungic. Conf., 1st, 1961, 2, 507). Introduced by Montecatini S.p.A. (later Montedison S.p.A.). APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact, ingested and systemic insecticide and acaricide. PRODUCTS: Discontinued products ‘Tartan’* (Montedison). Supplementary Entries – Extended cyclafuramid 147 MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T+; R28| T; R24 Details PM5, p. 138. cybutryne Algistat NOMENCLATURE: Common name cybutryne (BSI, E-ISO, (m) F-ISO) IUPAC name N 2 -tert-butyl-N 4 -cyclopropyl-6-methylthio-1,3,5-triazine-2,4-diamine Chemical Abstracts name N-cyclopropyl-N′-(1,1-dimethylethyl)- 6-(methylthio)-1,3,5-triazine-2,4-diamine CAS RN [28159–98–0] Smiles code CC(NC1=NC(NC2CC2)=NC(SC)=N1)(C)C PHYSICAL CHEMISTRY: Mol. wt. 253.4 M.f. C 11 H 19 N 5 S COMMERCIALISATION: Manufacturers Zhejiang Zhongshan; Ciba PRODUCTS: Other products ‘Irgarol 1510’ (Ciba Specialty Chemicals). cyclafuramid Fungicide NOMENCLATURE: Common name cyclafuramid (BSI, E-ISO); cyclafuramide ((m) F-ISO) IUPAC name N-cyclohexyl-2,5-dimethyl-3-furamide Chemical Abstracts name N-cyclohexyl-2,5-dimethyl-3-furancarboxamide CAS RN [34849–42–8] Development codes BAS 327F (BASF) Smiles code Cc1cc(C(=O)NC2CCCCC2)c(C)o1 PHYSICAL CHEMISTRY: Mol. wt. 221.3 M.f. C 13 H 19 NO 2 COMMERCIALISATION: History Fungicide introduced by BASF AG. N N N N H SCH 3 N H C(CH 3 ) 3 148 The Pesticide Manual Sixteenth Edition © BCPC 2012 cycloheximide cycloheximide Fungicide, plant growth regulator NOMENCLATURE: Common name cycloheximide (BSI, E-ISO, (m) F-ISO) IUPAC name 3-[(2R)-2-[(1S,3S,5S)-3,5-dimethyl-2-oxocyclohexyl]-2-hydroxyethyl] glutarimide Chemical Abstracts name [1S-[1α(S*),3α,5β]]-4-[2-(3,5-dimethyl-2-oxocyclohexyl)-2- hydroxyethyl]-2,6-piperidinedione CAS RN [66–81–9] Smiles code CC1CC(C)C(=O)C(C1)C(O)CC2CC(=O)NC(=O)C2 PHYSICAL CHEMISTRY: Mol. wt. 281.4 M.f. C 15 H 23 NO 4 Form Colourless crystals. M.p. 115.5–117 °C Solubility In water 21 g/l (2 °C). Soluble in chloroform, isopropanol, other common organic solvents; sparingly soluble in saturated hydrocarbons. Stability Stable in neutral or acid solution, but rapidly decomposed by alkali at room temperature to form 2,4-dimethylcyclohexanone. Specifc rotation [α]25D –6.8° (20 g/l water) COMMERCIALISATION: Production Produced in culture by Streptomyces griseus and was recovered as a by- product of streptomycin manufacture. History Antifungal antibiotic isolated by A. Whiffen et al. (J. Bacteriol., 1946, 52, 610), agricultural uses reviewed (J. H. Ford et al., Plant Dis. Rep., 1958, 42, 680). Introduced for crop protection by the Upjohn Co. (later Nor-Am.). APPLICATIONS: Uses It inhibits the growth, in culture, of many plant pathogenic fungi; it was used to control powdery mildews on ornamentals, rusts and leafspot on grasses. Its plant growth-regulating properties were used for promoting the abscission of fruit, e.g. olives and oranges. Formulation types WP. Compatibility Chlordane is reported to cause a rapid loss of activity. PRODUCTS: Discontinued products ‘ActiAid’* (Upjohn); ‘Actidione’* (Upjohn). ANALYSIS: Product analysis by bioassay (G. C. Prescott et al., J. Agric. Food Chem., 1956, 4, 343; W. W. Kilgore, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 3, 1). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.244 (1997). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2, mice 133, guinea pigs 65, monkeys 60 mg/kg. Toxicity Class WHO (a.i.) Ia EC Classifcation R68| R61| T+; R28| N; R51, R53 Details PM8, Entry 03600. Supplementary Entries – Extended cyometrinil 149 cycluron Herbicide NOMENCLATURE: Common name cycluron (BSI, E-ISO, (f) F-ISO, WSSA); COMU (JMAF) IUPAC name 3-cyclo-octyl-1,1-dimethylurea Chemical Abstracts name N′-cyclooctyl-N,N-dimethylurea Other names OMU CAS RN [2163–69–1] Smiles code CN(C)C(=O)NC1CCCCCCC1 PHYSICAL CHEMISTRY: Composition Tech. isc. 97%. Mol. wt. 198.3 M.f. C 11 H 22 N 2 O Form Colourless crystals. M.p. 138 °C; (tech., 134–138 °C) Solubility In water 1.1 g/l (20 °C). In acetone 67, benzene 55, methanol 500 (all in g/kg, 20 °C). COMMERCIALISATION: History Herbicide reported by A. Fischer (Z. Pfanzenkr. Pfanzenpathol. Pfanzenschutz, 1960, 67, 577). Introduced by BASF AG. Patents DE 1027930, DE 1062482. APPLICATIONS: Uses A mixture of cycluron and chlorbufam was used pre-em. at 3–6 l ‘Alipur’/ha to control annual weeds in sugar beet and vegetables. PRODUCTS: Discontinued mixtures ‘Alipur’* (+ chlorbufam) (BASF). ANALYSIS: Product analysis is by titration. Residues may be determined by glc of the dimethylamine produced by hydrolysis. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2600 mg/kg. Skin and eye There was no local irritation to the backs of ears of white rabbits treated (20 h) with an aqueous solution (500 g/l). Toxicity Class WHO (a.i.) U Details PM6, p. 141. cyometrinil Herbicide safener NOMENCLATURE: Common name cyomé(trinil) ((m) F-ISO); cyometrinil (BSI, WSSA, E-ISO) IUPAC name (Z)-cyanomethoxyimino(phenyl)acetonitrile Chemical Abstracts name (Z)-α-[cyanomethoxyimino]benzeneacetonitrile CAS RN [78370–21–5] (Z)- isomer; [63278–33–1] unstated stereochemistry Development codes CGA 43 089 Smiles code N#CCON=C(C#N)c1ccccc1 150 The Pesticide Manual Sixteenth Edition © BCPC 2012 cypendazole PHYSICAL CHEMISTRY: Mol. wt. 185.2 M.f. C 10 H 7 N 3 O Form Colourless crystals. M.p. 55–56 °C V.p. 0.0465 mPa (20 °C) Henry 9.07 × 10 –5 Pa m 3 mol –1 (calc.) S.g./ density 1.260 Solubility In water 95 mg/l (20 °C). In benzene 550, dichloromethane 700, methanol 230, isopropanol 74 (all in g/kg, 20 °C). Stability DT 50 (calc.) >200 d (pH 5–7), 19.4 d (pH 9) (20 °C). Exothermic decomposition >300 °C. COMMERCIALISATION: History Herbicide safener for 2-chloroacetanilides, introduced by Ciba-Geigy AG. Patents BE 845827, GB 1524596. APPLICATIONS: Biochemistry Enhances cytochrome P450-mediated oxidative metabolism of the herbicide (see J. Davies & J. C. Caseley, Pestic. Sci. 1999, 55(11) 1043–1058). Uses Increases the tolerance of some crop plants to chloroacetanilide herbicides. PRODUCTS: Discontinued products ‘Concep’* (Ciba-Geigy). ANALYSIS: Product analysis is by glc. Residues are determined by glc using TID. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2277 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats >3100 mg/kg. Non-irritant to skin and eyes (rabbits). NOEL (90 d) for dogs >100 mg/kg diet (3.1 mg/kg daily). Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds In laboratory trials it is slightly toxic to birds. Fish LC 50 (96 h) for rainbow trout 5.6, carp 11.7, bluegill 10.9 mg/l. Details PM7, Entry 03670. cypendazole Fungicide NOMENCLATURE: Common name cypendazole (BSI, E-ISO, (m) F-ISO, JMAF) IUPAC name methyl 1-(5-cyanopentylcarbamoyl)benzimidazol-2-ylcarbamate Chemical Abstracts name methyl [1-[[(5-cyanopentyl)amino]carbonyl]-1H- benzimidazol-2-yl]carbamate CAS RN [28559–00–4] Development codes DAM 18 654 Smiles code COC(=O)Nc1nc2ccccc2n1C(=O)NCCCCCC#N PHYSICAL CHEMISTRY: Mol. wt. 329.4 M.f. C 16 H 19 N 5 O 3 COMMERCIALISATION: History Systemic fungicide introduced by Bayer AG. Supplementary Entries – Extended cyprazine 151 APPLICATIONS: Mode of action Systemic fungicide. PRODUCTS: Discontinued products ‘Folicidin’* (Bayer). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Details PM4, p. 145. cyperquat; cyperquat chloride Herbicide NOMENCLATURE: Common name cyperquat (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name 1-methyl-4-phenylpyridinium (I) Chemical Abstracts name (I) CAS RN [48134–75–4] cyperquat; [39794–99–5] cyperquat chloride Development codes S 21 634 PHYSICAL CHEMISTRY: Mol. wt. 170.2; (cyperquat chloride 205.7) M.f. C 12 H 12 N; (cyperquat chloride C 12 H 12 ClN) COMMERCIALISATION: History Cyperquat chloride introduced as a herbicide by Gulf Oil Chemicals. cyprazine Herbicide NOMENCLATURE: Common name cyprazine (BSI, E-ISO, (f) F-ISO, ANSI, WSSA) IUPAC name 6-chloro-N 2 -cyclopropyl-N 4 -isopropyl-1,3,5-triazine-2,4-diamine; 2-chloro- 4-cyclopropylamino-6-isopropylamino-1,3,5-triazine Chemical Abstracts name 6-chloro-N-cyclopropyl-N′-(1-methylethyl)-1,3,5-triazine-2,4- diamine CAS RN [22936–86–3] Development codes S 6115 Smiles code CC(C)Nc1nc(Cl)nc(NC2CC2)n1 PHYSICAL CHEMISTRY: Mol. wt. 227.7 M.f. C 9 H 14 ClN 5 COMMERCIALISATION: History Herbicide reported by O. C. Burnside et al. (Proc. North Cent. Weed Control Conf., 1969, p. 21). Introduced by Gulf Oil Corp. PRODUCTS: Discontinued products ‘Outfox’* (Gulf); Discontinued mixtures ‘Prefox’* (+ ethiolate) (Gulf). Details PM4, p. 146. 152 The Pesticide Manual Sixteenth Edition © BCPC 2012 cyprofuram cyprazole Herbicide NOMENCLATURE: Common name cyprazole (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name N-[5-(2-chloro-1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl] cyclopropanecarboxamide (I) Chemical Abstracts name (I) CAS RN [42089–03–2] Development codes S 19 073 Smiles code CC(C)(CCl)c1nnc(NC(=O)C2CC2)s1 PHYSICAL CHEMISTRY: Mol. wt. 259.8 M.f. C 10 H 14 ClN 3 OS COMMERCIALISATION: History Herbicide introduced by Gulf Oil Chemicals. cyprofuram Fungicide NOMENCLATURE: Common name cyprofuram (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name (±)-α-[N-(3-chlorophenyl)cyclopropanecarboxamido]-γ-butyrolactone Chemical Abstracts name N-(3-chlorophenyl)-N-(tetrahydro-2-oxo-3-furanyl) cyclopropanecarboxamide CAS RN [69581–33–5] unstated stereochemistry EC no 274–050–9 Development codes SN 78 314 (Schering) Smiles code Clc1cccc(c1)N(C2CCOC2=O)C(=O)C3CC3 PHYSICAL CHEMISTRY: Mol. wt. 279.7 M.f. C 14 H 14 ClNO 3 Form Colourless crystalline solid. M.p. 95–96 °C V.p. 0.0066 mPa (25 °C) Solubility In water 574 mg/l (room temperature). In acetone, dichloromethane 500, cyclohexanone 330, ethanol 50, n-octanol 17, xylene 60 (all in g/kg, room temperature). Stability Stable in acid media, but hydrolysed under alkaline conditions; DT 50 37 d (pH 7), 12 h (pH 9) (25 °C). COMMERCIALISATION: History Fungicide reported by D. Baumert & H. Buschhaus (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1982, 47, 979). Introduced by Schering AG. Patents GB 1603730 APPLICATIONS: Mode of action Systemic fungicide. Uses Active against Oomycetes. It was recommended against Plasmopara viticola and Phytophthora infestans but only in combination with contact fungicides. PRODUCTS: Discontinued products ‘Vinicur’* (Schering). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. Supplementary Entries – Extended DAEP 153 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 174, mice 296–314 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >1000 mg/kg. Toxicity Class WHO (a.i.) II EC Classifcation T; R25| Xn; R21| N; R50, R53 Details PM8, Entry 03740. cypromid Herbicide NOMENCLATURE: Common name cypromid (BSI, E-ISO, ANSI, WSSA, JMAF); cypromide ((f) F-ISO) IUPAC name 3′,4′-dichlorocyclopropanecarboxanilide Chemical Abstracts name N-(3,4-dichlorophenyl)cyclopropanecarboxamide CAS RN [2759–71–9] Development codes S 6000 Smiles code Clc1ccc(NC(=O)C2CC2)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 230.1 M.f. C 10 H 9 Cl 2 NO COMMERCIALISATION: History Herbicide reported by T. R. Hopkins et al. (Proc. Symp. New Herbic., 2nd, Paris, 1965, p. 187). Introduced by Gulf Oil Corp. APPLICATIONS: Mode of action Contact herbicide. PRODUCTS: Discontinued products ‘Clobber’* (Gulf). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Details PM3, p. 148. DAEP Insecticide IRAC 1B NOMENCLATURE: Common name DAEP (JMAF) IUPAC name N-(2-dimethoxyphosphinothioylthioethyl)acetamide; S-2-acetamidoethyl O,O-dimethyl phosphorodithioate Chemical Abstracts name S-[2-(acetylamino)ethyl] O,O-dimethyl phosphorodithioate CAS RN [13265–60–6] Smiles code COP(=S)(OC)SCCNC(=O)C PHYSICAL CHEMISTRY: Mol. wt. 243.3 M.f. C 6 H 14 NO 3 PS 2 154 The Pesticide Manual Sixteenth Edition © BCPC 2012 decafentin COMMERCIALISATION: History Insecticide developed by Nippon Soda Co., Ltd. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Amiphos’* (Nippon Soda). DCPM Acaricide NOMENCLATURE: Common name DCPM (JMAF) IUPAC name bis(4-chlorophenoxy)methane Chemical Abstracts name 1,1′-[methylenebis(oxy)]bis[4-chlorobenzene] Other names oxythane CAS RN [555–89–5] Development codes K-1875 Smiles code Clc1ccc(OCOc2ccc(Cl)cc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 269.1 M.f. C 13 H 10 Cl 2 O 2 COMMERCIALISATION: History Acaricide reported by L. R. Jeppson (J. Econ. Entomol., 1946, 39, 813). Introduced by Dow Chemical Co. (later DowElanco). PRODUCTS: Discontinued products ‘Neotran’* (Dow). decafentin Fungicide NOMENCLATURE: Common name decafentin (BSI, E-ISO, (m) F-ISO) IUPAC name decyltriphenylphosphonium bromochlorotriphenylstannate(IV) Chemical Abstracts name (TB-5–12)-decyltriphenylphosphonium bromochlorotriphenylstannate(1-) CAS RN [15652–38–7] Development codes A 36 Smiles code CCCCCCCCCC[P+](c1ccccc1)(c2ccccc2)c3ccccc3.Cl[Sn-](Br)(c1ccccc1) (c2ccccc2)c3ccccc3 PHYSICAL CHEMISTRY: Mol. wt. 868.9 M.f. C 46 H 51 BrClPSn COMMERCIALISATION: History Fungicide introduced by Celamerck GmbH & Co. (later Shell Agrar). PRODUCTS: Discontinued products ‘Stanoram’* (Shell Agrar). Supplementary Entries – Extended defenuron 155 decarbofuran Insecticide NOMENCLATURE: Common name decarbofuran (BSI, E-ISO, (m) F-ISO) IUPAC name 2,3-dihydro-2-methylbenzofuran-7-yl methylcarbamate Chemical Abstracts name 2,3-dihydro-2-methyl-7-benzofuranyl methylcarbamate CAS RN [1563–67–3] Development codes BAY 62 863 Smiles code CNC(=O)Oc1cccc2CC(C)Oc21 PHYSICAL CHEMISTRY: Mol. wt. 207.2 M.f. C 11 H 13 NO 3 COMMERCIALISATION: History Insecticide evaluated by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. MAMMALIAN TOXICOLOGY: EC Classifcation T; R23/24/25 defenuron Herbicide NOMENCLATURE: Chemical Abstracts name N-phenyl-N′-methylurea CAS RN [1007–36–9] Development codes IPO 4328 PHYSICAL CHEMISTRY: Mol. wt. 150.2 M.f. C 8 H 10 N 2 O Form Colourless crystals. M.p. 148–149.5 °C V.p. 1 × 10-2 mPa (20 °C) Henry 1.18 × 10 –6 Pa m 3 mol –1 (20 °C, calc.) S.g./density 1.222 (25 °C) Solubility In water 1.27 g/l (20 °C). In ethanol 7.2 g/l, benzene 0.1 g/100 g, methylene chloride 0.331 g/100 g (all at 23 °C). COMMERCIALISATION: Manufacturers Fahlberg-List APPLICATIONS: Biochemistry Inhibits photosynthesis. Mode of action Active by both leaf and root uptake. Uses Control of weeds in potatoes, cereals, maize, sunfower, peas, vines, fruit and forestry; used in combination with triazine or other herbicides. Formulation types WP. ANALYSIS: Product by acid hydrolysis with a mixture of sulfuric and phosphoric acids; made alkaline and the liberated methylamine distilled off and measured by titration. Residues by extraction with methanol, clean up by column chromatography; then acid hydrolysis, diazotisation and coupling of the aniline with N-(1-naphthyl)ethylenediamine, followed by determination by tlc or colorimetry. 156 The Pesticide Manual Sixteenth Edition © BCPC 2012 dehydroacetic acid MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3440 mg/kg. NOEL (90 d) for rats 180 mg/kg daily. ECOTOXICOLOGY: Fish LC 50 (120 h) for guppies 172 mg/l. ENVIRONMENTAL FATE: Plants Metabolism is by N-demethylation to N-phenylurea; both parent and metabolite are conjugated as glycosides. dehydroacetic acid Fungicide NOMENCLATURE: IUPAC name 2-acetyl-5-methyl-3-oxopent-4-en-5-olide (i); 3-acetyl-6-methylpyran-2,4- dione (ii) Chemical Abstracts name 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione (i); 3-acetyl-4-hydroxy-6-methyl-2H-pyran-2-one (ii); 3-acetyl-2-hydroxy-6-methyl-4H- pyran-4-one (iii) Other names DHA CAS RN [520–45–6] (i); [771–03–9] (ii); [16807–48–0] (iii); [4418–26–2] sodium salt EC no 208–293–9; 224–580–1 sodium salt Smiles code CC(=O)C1C(=O)OC(=CC1=O)C PHYSICAL CHEMISTRY: Mol. wt. 168.2 M.f. C 8 H 8 O 4 Form Colourless powder. M.p. 109–111 °C (subliming) B.p. 269 °C V.p. 2.5 × 10 5 mPa (100 °C) Solubility In water 330 g/kg (25 °C). In propylene glycol 480, methanol 140 (both g/kg, 25 °C); sparingly soluble in non-hydroxylic organic solvents. COMMERCIALISATION: History Long-known as a chemical, fungicidal activity reported by P. A. Wolf (Food Technol. (Chicago), 1950, 4, 294). Introduced by Dow Chemical Co. APPLICATIONS: Uses Fungicide for prevention of mould growth on fresh and dried fruit and vegetables, and for impregnation of food wrappings. ANALYSIS: Residue analysis is by extraction wth chloroform from acid solution, measuring the optical density at 307 nm. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1000 mg/kg. Sodium salt: Acute oral LD 50 for rats 1000 mg/kg. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22. (Sodium salt Xn; R22) Details PM6, p. 152. Supplementary Entries – Extended demephion; demephion-O; demephion-S 157 delachlor Herbicide NOMENCLATURE: Common name delachlor (BSI, E-ISO, ANSI); dé(lachlore) ((m) F-ISO) IUPAC name 2-chloro-N-(isobutoxymethyl)acet-2′,6′-xylidide Chemical Abstracts name 2-chloro-N-(2,6-dimethylphenyl)-N-[(2-methylpropoxy) methyl]acetamide CAS RN [24353–58–0] Development codes CP 52 223 Smiles code CC(C)COCN(C(=O)CCl)c1c(C)cccc1C PHYSICAL CHEMISTRY: Mol. wt. 283.8 M.f. C 15 H 22 ClNO 2 COMMERCIALISATION: History Herbicide reported by R. F. Husted et al. (Proc. North Cent. Weed Control Conf., 1967). Introduced by Monsanto Co. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Details PM2, p. 100. demephion; demephion-O; demephion-S Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name demephion (for a reaction product comprising demephion-O and demephion-S) (BSI); demephion-O (i), demephion-S (ii) (for thiono and thiolo isomers, respy.) (BSI, E-ISO, (m) F-ISO) IUPAC name (i) O,O-dimethyl O-2-methylthioethyl phosphorothioate; (ii) O,O-dimethyl S-2-methylthioethyl phosphorothioate Chemical Abstracts name (i) O,O-dimethyl O-[2-(methylthio)ethyl] phosphorothioate; (ii) O,O-dimethyl S-[2-(methylthio)ethyl] phosphorothioate Other names methyl- demeton-methyl CAS RN [682–80–4] (i); [2587–90–8] (ii); [8065–62–1] (i) + (ii) EC no 211–666–9 (i); 219–971–9 (ii) PHYSICAL CHEMISTRY: Mol. wt. 216.3 M.f. C 5 H 13 O 3 PS 2 Form Straw-coloured liquid. B.p. 107 °C (decomp.)/ 0.1 mmHg (i); 65 °C (decomp.)/0.1 mmHg (ii) S.g./density 1.198 (20 °C) (i); 1.218 (25 °C) (ii) Solubility In water 300 mg/l (i), 3000 mg/l (ii) (both room temperature). The mixture is miscible with most aromatic solvents, chlorobenzene and ketones; immiscible with most aliphatic hydrocarbons. COMMERCIALISATION: History Systemic acaricide and insecticide reported by H. Rueppold (Wiss. Z. Martin- Luther Univ. Halle-Wittenberg Math.-Naturwiss. Reihe, 1955, 5, 219). Introduced initially by VEB Farbenfabrik Wolfen. Patents DE 1014017. 158 The Pesticide Manual Sixteenth Edition © BCPC 2012 demeton; demeton-O; demeton-S APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide. Uses Effective against sucking insects, at 170–510 g/ha. Compatibility Not compatible with strongly alkaline pesticides. PRODUCTS: Discontinued products ‘Atlasetox’* (Atlas); ‘Cymetox’* (Cyanamid); ‘Pyracide’* (BASF); ‘Tinox’* (E. Europe) (VEB Farbenfabrik Wolfen). ANALYSIS: Product analysis by separating the two isomers using column chromatography; demephion-O is then oxidised by perchloric acid and determined as phosphate; demephion-S is hydrolysed by alkali, the solution acidifed and titrated with iodine. Residue analysis is by isolation and oxidation to phosphate, which is measured colorimetrically by standard procedures. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R28| T; R24 (for (i) or (ii)) ENVIRONMENTAL FATE: Plants Metabolised in plants to the sulfoxide, then slowly to the sulfone and to phosphates. Details PM6, p. 153. demeton; demeton-O; demeton-S Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name mercaptofos* (i) (USSR); mercaptofos teolevy* (ii) (USSR); mercaptostiol (ii) (USSR); mercaptofostion (i) (USSR); demeton-O (i), demeton-S (ii) (for thiono and thiolo isomers, respy.) (BSI, E-ISO, (m) F-ISO); demeton (for a reaction product comprising demeton-O and demeton-S) (BSI, ESA) IUPAC name (i) O,O-diethyl O-2-ethylthioethyl phosphorothioate; (ii) O,O-diethyl S-2- ethylthioethyl phosphorothioate Chemical Abstracts name (i) O,O-diethyl O-[2-(ethylthio)ethyl] phosphorothioate; (ii) O,O-diethyl S-[2-(ethylthio)ethyl] phosphorothioate Other names diethyl 2-ethylthioethyl phosphorothionate (i); diethyl 2-ethylthioethyl phosphorothiolate (ii) CAS RN [298– 03–3] demeton-O; [126–75–0] demeton-S; [8065–48–3] demeton, formerly [8000–97–3] EC no 206–053–8 demeton-O; 204–801–8 demeton-S Development codes Bayer 10 756; E-1059 PHYSICAL CHEMISTRY: Composition Reaction of 2-ethylthioethanol with O,O-diethyl phosphorochloridothioate gives demeton asc. 65:35 mixture of (i) and (ii). Mol. wt. 258.3 M.f. C 8 H 19 O 3 PS 2 Supplementary Entries – Extended demeton; demeton-O; demeton-S 159 Form Pure demeton-O (i) and demeton-S (ii) are colourless oils. Tech. mixture is a light yellow oil with a pronounced mercaptan-like odour. B.p. 123 °C /1 mmHg (demeton-O); 128 °C /1 mmHg (demeton-S) V.p. 38 mPa (20 °C, demeton-O); 35 mPa (20 °C, demeton-S) Henry demeton-O; 1.64 × 10 –1 Pa m 3 mol –1 (20 °C, calc.); demeton-S: 4.52 × 10 –3 Pa m 3 mol –1 (20 °C, calc.) S.g./density demeton-O 1.119 (21 °C); demeton-S 1.132 (21 °C) Solubility Demeton-O (i) (room temperature): 60 mg/l water; soluble in most organic solvents. Demeton-S (ii) (room temperature): 2 g/l water; soluble in most organic solvents. Stability Demeton is hydrolysed by concentrated alkali, but is compatible with most non-alkaline pesticides except water-soluble mercury compounds. The mechanism of isomerisation of (i) to (ii) was examined by T. R. Fukuto & R. L. Metcalf (J. Am. Chem. Soc., 1954, 76, 5103) and the self-alkylation of demeton described by D. F. Heath, (Nature (London), 1957, 179, 377). COMMERCIALISATION: History Insecticide reported by G. Unterstenhöfer (Meded. Landbouwhogesch. Opzoekingsstn. Staat Gent, 1952, 17, 75). Introduced by Farbenfabriken Bayer AG (later Bayer AG). Patents DE 836349; US 2571989 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic and contact insecticide and acaricide, with some fumigant action. Demeton-S rapidly penetrates foliage. Uses Demeton is effective against sap-feeding insects and mites. Formulation types EC. Compatibility Demeton is compatible with most non-alkaline pesticides except water- soluble mercury compounds. PRODUCTS: Discontinued products ‘Isosystox’* (demeton-S) (Bayer); ‘Systox’* (demeton) (Bayer). ANALYSIS: Product analysis by glc (J. G. F. Ernst, J. Chromatogr., 1977, 133, 245) or by alkaline hydrolysis and titration of the excess of alkali (CIPAC Handbook, 1970, 1, 302) or of the thiol with iodine (ibid., 1980, 1A, 1198). Residues determined by glc (D. C. Abbott et al., Pestic. Sci., 1970, 1, 10; A. Ambrus et al., J. Assoc. Off. Anal. Chem., 1981, 64, 733) or by oxidation to phosphoric acid which is measured by standard colorimetric procedures (D. MacDougall, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 2, 451; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 483). See also Pestic. Anal. Man., I, 302. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 25 (1975), 27 (1976), 43 (1984). PDS 60 (1987). ICSC.861 (demeton mixed isomers; 2002); ICSC.864 (demeton-O-methyl; 2006). MAMMALIAN TOXICOLOGY: Oral Demeton: Acute oral LD 50 for male rats 6–12, female rats 2.5–4.0 mg/kg. Demeton-O: Acute oral LD 50 for male rats 30 mg/kg. Demeton-S: Acute oral LD 50 for rats 1.5 mg/ kg. Demeton-S sulfoxide: Acute oral LD 50 for rats 2.3 mg/kg. Demeton-S sulfone: Acute oral LD 50 for rats 1.9 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats 14 mg demeton/kg. NOEL (1.83 y) for rats 2 mg/kg diet (0.1 mg/kg daily) (WHO Pestic. Residue 160 The Pesticide Manual Sixteenth Edition © BCPC 2012 demeton-S-methylsulphon Ser., 1974, 3, 217). ADI/RfD (JMPR) No ADI [1984]; (EPA) cRfD 0.00004 mg/kg b.w. [1988] (demeton). Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R27/28| N; R50 (demeton-O and demeton): T+; R27/28 (demeton-S) ENVIRONMENTAL FATE: Plants The thioether sulfur of both isomers is oxidised, metabolically, to the sulfoxide and sulfone (R. B. March et al., J. Econ. Entomol., 1955, 48, 355). Details PM8, Entry 03910 demeton-O-methyl Acaricide IRAC 1B NOMENCLATURE: CAS RN [867–27–6] EC no 212–758–1 PHYSICAL CHEMISTRY: Mol. wt. 230.3 M.f. C 6 H 15 O 3 PS 2 APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Knock-Out’* (Crop Health). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 27 (1976). ICSC.429 (1997). demeton-S-methylsulphon Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name demeton-S-methylsulphon (E-ISO); dé(mé) ((m) F-ISO); demeton-S- methyl sulphone (BSI) IUPAC name S-2-ethylsulfonylethyl O,O-dimethyl phosphorothioate Chemical Abstracts name S-[2-(ethylsulfonyl)ethyl] O,O-dimethyl phosphorothioate CAS RN [17040–19–6] EC no 241–109–5 Development codes Bayer 20 315; E 158; M3/158 Smiles code CCS(=O)(=O)CCSP(=O)(OC)OC PHYSICAL CHEMISTRY: Mol. wt. 262.3 M.f. C 6 H 15 O 5 PS 2 Form Colourless crystals. M.p. 51.6 °C B.p. 115 °C /0.0075 mmHg; 120 °C /0.03 mmHg V.p. 0.056 mPa (20 °C) CH 3 CH 2 SO 2 CH 2 CH 2 S P(OCH 3 ) 2 O Supplementary Entries – Extended demeton-S-methylsulphon 161 Henry >7.34 × 10-8 Pa m 3 mol –1 (calc.) S.g./density 1.416 (20 °C) Solubility In water >200 g/l (20 °C). Soluble in alcohols, ketones, and most chlorinated hydrocarbons, e.g. dichloromethane 200 g/l. In toluene 50–100 mg/l. Stability Hydrolysed slowly in acidic media, and rapidly in alkaline media. COMMERCIALISATION: History Insecticide introduced by Bayer AG. Patents DE 948241 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide with contact and stomach action. Uses Control of aphids, other sucking insects, sawfies, and spider mites. Was normally used in combination with azinphos-methyl on fruit, vines,ornamentals, potatoes, beet, cotton, and vegetables. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Metaisosystoxsulfon’* (Bayer). ANALYSIS: Product analysis by hydrolysis with alkali, the excess of which is determined by titration (CIPAC Handbook, 1970, 1, 312). Residues determined by glc (M. C. Bowman et al., J. Assoc. Off. Anal. Chem., 1969, 52, 157; J. H. van der Merwe & W. B. Taylor, Pfanz.-Nachr. Bayer (Engl. Ed.), 1971, 24, 259). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Mtg. 65 (1992); JMPR Evaln. I 66 (1992); JMPR Evaln. II 58 (1989) EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 37.5, micec. 30 mg/kg. Skin and eye Acute percutaneous LD 50 for ratsc. 500 mg/kg. Inhalation LC 50 (4 h) for ratsc. 0.2 mg/l air (aerosol). NOEL (2 y) for rats 1 mg/kg diet. ADI/RfD (JMPR) 0.0003 mg/kg b.w. for sum of demeton-S-methyl, demeton-S-methylsulphon and oxydemeton-methyl [1989]. Other Acute i.p. LD 50 for ratsc. 20.8 mg/kg. Toxicity Class WHO (a.i.) Ib EC Classifcation T; R25| Xn; R21| N; R51, R53 ECOTOXICOLOGY: Fish LC 50 for orfe 102 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, elimination is rapid, and predominantly in the urine. Plants In plants, metabolism involves oxidation and hydrolysis, giving dimethyl phosphate and phosphoric acid. 162 The Pesticide Manual Sixteenth Edition © BCPC 2012 desmetryn 2,4-DEP Herbicide NOMENCLATURE: Common name 2,4-DEP (WSSA) IUPAC name mixture of (i) tris[2-(2,4-dichlorophenoxy)ethyl] phosphite (I) and (ii) bis[2- (2,4-dichlorophenoxy)ethyl] phosphonate (II) Chemical Abstracts name (I) + (II) CAS RN [39420–34–3] (i) + (ii); [94–84–8] (i) Development codes 3Y9 PHYSICAL CHEMISTRY: Mol. wt. 649.1 (i); 460.1 (ii) M.f. C 24 H 21 Cl 6 O 6 P (i); C16H15Cl4O5P (ii) COMMERCIALISATION: History Herbicide introduced by Uniroyal Chemical Co., Inc. PRODUCTS: Discontinued products ‘Falone’* (Uniroyal). desmetryn Herbicide HRAC C1 WSSA 5; 1,3,5-triazine NOMENCLATURE: Common name no name (Portugal); desmetryn (BSI (since 1984), E-ISO, WSSA); desmetryne ((f) F-ISO, JMAF, BSI (before 1984)) IUPAC name N 2 -isopropyl-N4-methyl-6-methylthio-1,3,5-triazine-2,4-diamine Chemical Abstracts name N-methyl-N′-(1-methylethyl)-6-(methylthio)-1,3,5-triazine- 2,4-diamine CAS RN [1014–69–3] EC no 213–800–1 Development codes G 34 360 Smiles code CNc1nc(NC(C)C)nc(SC)n1 PHYSICAL CHEMISTRY: Composition Tech. is 95%. Mol. wt. 213.3 M.f. C 8 H 15 N 5 S Form White powder. M.p. 84– 86 °C B.p. 339 °C /98.4 kPa V.p. 0.133 mPa (20 °C) K ow logP = 2.38 Henry 4.8 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.172 (20 °C) Solubility In water 580 mg/l (20 °C). Readily soluble in most organic solvents, e.g. methanol 300, acetone 230, dichloromethane, toluene 200, hexane 2.6 (all in g/kg, 20 °C). Stability No signifcant hydrolysis at 70 °C detected at 5<pH<13. pKa 4.0, weak base N N N CH 3 S NHCH(CH 3 ) 2 NHCH 3 Supplementary Entries – Extended desmetryn 163 COMMERCIALISATION: History Herbicide reported by J. G. Elliott & T. I. Cox (Proc. Br. Weed Control Conf., 6th, 1962, 2, 759). Introduced by J. R. Geigy S.A. (later Novartis Crop Protection AG). Patents CH 337019; GB 814948 Manufacturers Novartis APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective systemic herbicide, absorbed by the leaves and roots, with translocation acropetally through the xylem, and accumulation in the apical meristems. Uses Post-emergence control of fat-hen (Chenopodium album) and other annual broad-leaved weeds and some grasses at 0.25–0.5 kg/ha in brassicas (except caulifowers and broccoli), herbs, onions, leeks, and conifer seedbeds. Formulation types WP. Compatibility There may be incompatibility with some insecticides. PRODUCTS: Discontinued products ‘Semeron’* (Novartis). ANALYSIS: Product analysis by glc (CIPAC Handbook, 1983, 1B, 1765). Residues determined by glc (K. Ramsteiner et al., J. Assoc. Off. Anal. Chem., 1974, 57, 192). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1390, mice 1750 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 2000 mg/kg. Not a skin or eye irritant (rabbits). Not a skin sensitiser when applied epidermally; skin sensitiser when applied intradermally (guinea pigs). Inhalation LC 50 (1 h) for rats >1563 mg/m 3 as WP 25. NOEL (90 d) for rats 20 mg/kg diet (1.5 mg/kg daily); for dogs 200 mg/kg diet (6.6 mg/kg daily). ADI/RfD (BfR) 0.0014 mg/kg b.w. [1993]. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R21/22| N; R50, R53 ECOTOXICOLOGY: Birds LC 50 (8 d) for Japanese quail >10 000 mg/kg. Fish LC 50 (96 h) for rainbow trout 2.2, common carp 37 mg/l. Daphnia LC 50 (48 h) 45 mg/l. Algae EC 50 (72 h) for Scenedesmus subspicatus 0.004 mg/l. Bees Not toxic to bees; LD 50 (oral) >197 μg/bee, (topical) >101 μg/bee. Worms LC 50 (14 d) for earthworms 160 mg/kg soil. ENVIRONMENTAL FATE: Animals Major pathways in animal metabolism are hydrolysis of the methylthio group to form the hydroxy derivative, sulfoxidation of the methylthio group, and side-chain dealkylation. Plants Major pathways in plant metabolism are the hydrolysis of the methylthio group to form the hydroxy derivative, conjugation with glutathione and side- chain dealkylation. Soil/Environment Degradation involves oxidation of the methylthio group to sulfoxide and sulfone, hydrolysis with the introduction of a 2-hydroxy group, dealkylation at the substituted amino groups, cleavage of the amine moiety, and ring 164 The Pesticide Manual Sixteenth Edition © BCPC 2012 dialifos opening. Duration of residual activity in soil isc. 3 months, DT 50 c. 50 d. K oc 150, moderately mobile in soil. Degradation in aquatic systems is caused by microbial processes; desmetryn is also removed from water by adsorption to the sediment. dialifos Acaricide, insecticide NOMENCLATURE: Common name dialifor (ANSI, ESA, JMAF); dialifos (BSI, E-ISO); dialiphos ((m) F-ISO) IUPAC name S-2-chloro-1-phthalimidoethyl O,O-diethyl phosphorodithioate; N-[2-chloro- 1-(diethoxyphosphinothioylthio)ethyl]phthalimide Chemical Abstracts name S-[2-chloro-1-(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl) ethyl] O,O-diethyl phosphorodithioate CAS RN [10311–84–9] EC no 233–689–3 Development codes Hercules 14503 Smiles code CCOP(=S)(OCC)SC(CCl)N1C(=O) c2ccccc2C1=O PHYSICAL CHEMISTRY: Mol. wt. 393.8 M.f. C 14 H 17 ClNO 4 PS 2 Form Colourless crystals. M.p. 67–69 °C V.p. 133 mPa (35 °C) Solubility Practically insoluble in water (<1 mg/l). In acetone 760, isophorone 400, chloroform 620, xylene 570, diethyl ether 500, ethanol <10, hexane <10 (all in g/kg, 20 °C). Stability Tech. is hydrolysed in alkaline media, DT 50 2.5 h (pH 8, room temperature). COMMERCIALISATION: History Insecticide reported by W. R. Cothran et al. (J. Econ. Entomol., 1967, 60, 1151). Introduced by Hercules Inc. (later Nor-Am Chemical Co.). Patents GB 1091738; US 3355353 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide and acaricide with contact, stomach, and respiratory action. Uses Control of chewing and sucking insects and spider mites on potatoes, vegetables, pome fruit, stone fruit, citrus fruit, vines, nut trees, cotton, beet, oilseed rape, and roses. Formulation types EC. PRODUCTS: Discontinued products ‘Torak’* (AgrEvo, Cyanamid). ANALYSIS: Product by glc and uv spectrophotometry. Residues by GLC with phosphorus-specifc TID (M. A. Luke et al., J. Assoc. Off. Anal. Chem. 1981, 64, 1187). S P(OCH 2 CH 3 ) 2 S N CH CH 2 Cl O O Supplementary Entries – Extended di-allate 165 TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. I 45 (1985); JMPR Evaln. 27 (1976). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 43–53, female rats 5, male mice 39, female mice 65, rabbits 58–71, male dogs 97 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 145 mg/kg. Mild skin and eye irritant (rabbits). NOEL In 90 d feeding trials, rats receiving 10 mg/kg diet showed inhibition of plasma and erythrocyte cholinesterases. ADI/RfD (JMPR) ADI withdrawn (1982). Toxicity Class WHO (a.i.) II EPA (formulation) I EC Classifcation T+; R28| T; R24| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks 940 mg/kg. Fish LC 50 (24 h) for rainbow trout 0.55–1.08 mg/l. Bees Low toxicity to honeybees, LD 50 0.034–0.038 mg/bee. di-allate Herbicide NOMENCLATURE: Common name di-allate (BSI, E-ISO); diallate ((m) F-ISO, WSSA) IUPAC name S-2,3-dichloroallyl diisopropylthiocarbamate Chemical Abstracts name S-(2,3-dichloro-2-propenyl) bis(1-methylethyl) carbamothioate CAS RN [2303–16–4] EC no 218–961–1 Development codes CP 15 336 (Monsanto) Smiles code CC(C)N(C(C)C)C(=O)SCC(=CCl)Cl PHYSICAL CHEMISTRY: Composition It exists as geometric isomers which have been separated (F. H. A. Rummens, Weed Sci., 1975, 23, 7). Mol. wt. 270.2 M.f. C 10 H 17 Cl 2 NOS Form Amber- coloured liquid. M.p. 25–30 °C; <0 °C ((Z)- isomer); 36 °C ((E)- isomer) B.p. 97 °C /0.15 mmHg V.p. 20 mPa (25 °C) K ow logP = 3.29 (Agchem. Desk Ref.) Henry 3.86 × 10 –1 Pa m 3 mol –1 (calc.) S.g./density 1.188 (25 °C) Solubility In water 14 mg/l (25 °C). Miscible with acetone, ethanol, ethyl acetate, kerosene, isopropanol, xylene. Stability Stable to uv light; decomposes >200 °C. Stable to hydrolysis. COMMERCIALISATION: History Herbicide reported by L. H. Hannah (Proc. North Cent. Weed Control Conf., 1959, p. 50). Introduced by Monsanto Co. Patents US 3330643; US 3330821 APPLICATIONS: Biochemistry Inhibits lipid metabolism. Mode of action Selective herbicide. It is absorbed by the emerging wild oat coleoptile, toxicity being mainly at cell division. Uses A pre- or post-planting incorporated herbicide which controls wild oats in barley, fax, forage legumes, lentils, maize, peas, potatoes, soya beans and sugar beet. The (E)- isomer is less effective than the (Z)- isomer in reducing height of wild oats (F. H. A. Rummens et al., Weed 166 The Pesticide Manual Sixteenth Edition © BCPC 2012 diamidafos Sci., 1975, 23, 11). Formulation types EC; GR . PRODUCTS: Discontinued products ‘Avadex’* (Monsanto); Discontinued mixtures ‘Pyradex’* (+ chloridazon) (BASF). ANALYSIS: Product analysis by glc. Residues determined by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 76 (1988); a general review of thiocarbamates. IARC 30 (1983). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for rats 395, dogs 510 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 2000–2500 mg/kg. Moderate irritant to skin and eyes (rabbits). NOEL In 90 d feeding trials, rats receiving 400 mg/kg diet suffered weight loss, irritability, hyperactivity and mild cardiac changes; but no death occurred at 1200 mg/kg diet. In beagle dogs, adverse effects were observed at 600, but not at 125 mg/day. ADI/RfD (EPA) 0.005 mg/kg b.w. [1989]. Toxicity Class WHO (a.i.) II EC Classifcation Xn; R22| R40| N; R50, R53 ENVIRONMENTAL FATE: Soil/Environment It competes with moisture for adsorption on soil; loss is mainly by microbial breakdown, DT 50 30 d, provided it is fully incorporated in the soil. diamidafos Insecticide, nematicide IRAC 1B NOMENCLATURE: Common name diamidafos (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name phenyl N,N′-dimethylphosphorodiamidate (I) Chemical Abstracts name (I) CAS RN [1754–58–1] Development codes Dowco 169 Smiles code CNP(=O)(NC)Oc1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 200.2 M.f. C 8 H 13 N 2 O 2 P COMMERCIALISATION: History Nematicide reported by C. R. Youngson & C. A. I. Goring (Down Earth, 1963, 18(4), 3). Introduced by Dow Chemical Co. (later DowElanco). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Nellite’* (DowElanco). Supplementary Entries – Extended 1,2-dibromo-3-chloropropane 167 MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O diammonium ethylenebis(dithiocarbamate) Fungicide multi-site: alkylenebis(dithiocarbamate) NOMENCLATURE: IUPAC name diammonium ethylenebis(dithiocarbamate) Chemical Abstracts name diammonium 1,2-ethanediylbis[carbamodithioate] Other names amobam; amobam T (for the di-trolamine (bis-triethanolammonium) salt) CAS RN [3566–10–7]; [33233–06–6] di-trolamine salt Smiles code [S-]C(=S)NCCNC(=S)[S-].[NH4+].[NH4+] PHYSICAL CHEMISTRY: Mol. wt. 246.4 M.f. C 4 H 14 N 4 S 4 M.p. 72.5–72.8 °C Solubility Soluble in water. Insoluble in xylene. COMMERCIALISATION: History Fungicide related to nabam and other dithiocarbamates. Manufactured and sold principally in China. APPLICATIONS: Biochemistry Non-specifc thiol reactant, inhibiting respiration. Mode of action Broad spectrum fungicide with protectant and curative action. Uses For control of spot disease, anthracnose and mildew, on various crops such as rice, rubber, millet, sweet potato, cucumber, cabbage and maize. Formulation types SL . PRODUCTS: Discontinued products ‘Amobam’* (Fike); ‘Chem-O-Bam’* (Tifa). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Mtg. 68 (1993); JMPR Evaln. I 69 (1993); JMPR Evaln. II 70 (1993) for metabolite ethylenethiourea. 1,2-dibromo-3-chloropropane Nematicide NOMENCLATURE: Common name DBCP (JMAF) IUPAC name 1,2-dibromo-3-chloropropane (I) CH 2 CH 2 C NH S S C NH S S NH 4 NH 4 168 The Pesticide Manual Sixteenth Edition © BCPC 2012 dibutyl adipate Chemical Abstracts name (I) CAS RN [96–12–8] EC no 202–479–3 Development codes OS1897 (Shell) Smiles code ClCC(Br)CBr PHYSICAL CHEMISTRY: Mol. wt. 236.3 M.f. C 3 H 5 Br 2 Cl Form Amber to dark brown liquid, with a mildly pungent odour. B.p. 196 °C V.p. 1.07 × 10 5 mPa (21 °C) K ow logP = 2.63 (Agchem. Desk Ref.) Henry 2.53 × 101 Pa m 3 mol –1 (calc.) S.g./density 2.08 (20 °C) Solubility In water 1g/kg (room temperature). Miscible with hydrocarbon oils, acetone, iso-propanol, methanol, 1,3-dichloropropane and 1,1,2-trichlorethane. Stability Stable in neutral and acidic media; converted to 2-bromoallyl alcohol in alkali. COMMERCIALISATION: History Nematicidal activity reported by C. W. McBeth & G. B. Bergeson (Plant Dis. Rep., 1955, 39, 223). Introduced by Dow Chemical Co. (later DowElanco) and Shell Development Co. APPLICATIONS: Uses Soil fumigant and nematicide, effective against a wide range of nematodes, including root-knot nematodes, at 10–125 kg/ha. Phytotoxicity Many perennial plants tolerate high concentrations, but others, including potatoes and tobacco, require a long aeration period before planting. PRODUCTS: Discontinued products ‘Fumazone’* (Dow); ‘Nemagon’* (Shell). ANALYSIS: Residues in drinking water by glc with linearised ECD (AOAC Methods, 18th Ed., 993.15). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.002 (2002). IARC 20 (1979); Suppl. 7 (1987); 71 (1999). MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 170–300, mice 260–400 mg/kg. Water GV 0.001 mg/l (see note on carcinogens). Other Causes sterility in humans and is mutagenic and carcinogenic in animals. Toxicity Class WHO (a.i.) Ia EC Classifcation R45; R46; R60| T; R25| Xn; R48/20/22| R52, R53 ENVIRONMENTAL FATE: Soil/Environment Does not persist is soil to the extent that it presents an accumulation problem. dibutyl adipate Insect repellent NOMENCLATURE: IUPAC name dibutyl adipate Chemical Abstracts name dibutyl hexanedioate CAS RN [105–99–7] Development codes Experimental Tick Repellent 3 Smiles code CCCCOC(=O) CCCCC(=O)OCCCC Supplementary Entries – Extended dibutyl succinate 169 PHYSICAL CHEMISTRY: Mol. wt. 258.4 M.f. C 14 H 26 O 4 COMMERCIALISATION: History Insect repellent introduced by Union Carbide Corp. (later Rhône-Poulenc Agrochimie). dibutyl phthalate Insect repellent NOMENCLATURE: Common name dibutyl phthalate (BSI, E-ISO); phtalate de butyle (F-ISO); () IUPAC name dibutyl phthalate Chemical Abstracts name dibutyl 1,2-benzenedicarboxylate Other names DBP CAS RN [84–74–2] Smiles code CCCCOC(=O)c1ccccc1C(=O)OCCCC PHYSICAL CHEMISTRY: Mol. wt. 278.4 M.f. C 16 H 22 O 4 COMMERCIALISATION: History Activity as insect repellent reported by F. M. Snyder & F. A. Morton (J. Econ. Entomol., 1947, 40, 586). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 189 (1997). ICSC.036 (2002). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O dibutyl succinate Insect repellent NOMENCLATURE: IUPAC name dibutyl succinate Chemical Abstracts name dibutyl butanedioate CAS RN [141–03–7] Smiles code CCCCOC(=O)CCC(=O)OCCCC PHYSICAL CHEMISTRY: Mol. wt. 230.3 M.f. C 12 H 22 O 4 COMMERCIALISATION: History Insect repellent introduced by Glenn Chemical Co. PRODUCTS: Discontinued products ‘Tabatrex’* (Glenn); ‘Tabutrex’* (Glenn). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O 170 The Pesticide Manual Sixteenth Edition © BCPC 2012 dicapthon dicamba-methyl Plant growth regulator NOMENCLATURE: Common name disugran (ANSI); dicamba-methyl (BSI, E-ISO, (m) F-ISO) IUPAC name methyl 3,6-dichloro-o-anisate Chemical Abstracts name methyl 3,6-dichloro-2-methoxybenzoate CAS RN [6597– 78–0] Smiles code COC(=O)c1c(Cl)ccc(Cl)c1OC PHYSICAL CHEMISTRY: Mol. wt. 235.1 M.f. C 9 H 8 Cl 2 O 3 COMMERCIALISATION: History Plant growth regulator introduced by Velsicol Chemical Co. (later Sandoz AG). PRODUCTS: Discontinued products ‘Racuza’* (Sandoz). dicapthon Insecticide IRAC 1B NOMENCLATURE: Common name dicapthon (ESA, ex-ANSI) IUPAC name O-2-chloro-4-nitrophenyl O,O-dimethyl phosphorothioate Chemical Abstracts name O-(2-chloro-4-nitrophenyl) O,O-dimethyl phosphorothioate CAS RN [2463–84–5] Development codes AC 4124 Smiles code COP(=S)(OC) Oc1ccc(cc1Cl)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 297.7 M.f. C 8 H 9 ClNO 5 PS COMMERCIALISATION: History Insecticide reported by T. B. Davich & J. W. Apple (J. Econ. Entomol., 1951, 44, 528) and by J. C. Gaines (ibid., p. 750). Introduced by American Cyanamid Co. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Dicapton’* (Cyanamid). Supplementary Entries – Extended dichlone 171 dichlone Algicide, fungicide NOMENCLATURE: Common name dichlone (BSI, E-ISO, (m) F-ISO, JMAF) IUPAC name 2,3-dichloro-1,4-naphthoquinone Chemical Abstracts name 2,3-dichloro-1,4-naphthalenedione CAS RN [117– 80–6] EC no 204–210–5 Development codes USR 604 (to Uniroyal) Smiles code ClC1=C(Cl)C(=O)c2ccccc2C1=O PHYSICAL CHEMISTRY: Composition Tech. isc. 95%. Mol. wt. 227.0 M.f. C 10 H 4 Cl 2 O 2 Form Yellow crystals. M.p. 193 °C (subliming >32 °C); tech., ≥188 °C B.p. 275 °C /2 mmHg V.p. 0.01 mPa (ARS PPD) K ow logP = 5.62 (Agchem. Desk Ref.) Solubility In water 0.1 mg/l (25 °C). In xylene and 1,2-dichlorobenzene,c. 4%. Moderately soluble in acetone, diethyl ether, benzene, ethyl acetate, acetic acid, DMF, and dioxane. Sparingly soluble in alcohols. Stability In the dry state, stable to light and heat. In solution, slowly decomposed by light. Stable in acidic media, but hydrolysed by alkalis. COMMERCIALISATION: History Fungicidal properties of this established chemical reported by W. P. ter Horst & E. L. Felix (Ind. Eng. Chem., 1943, 35, 1255). Introduced by Uniroyal Chemical Co., Inc. and by FMC Corp. Patents US 2302384; US 2349772 (to Uniroyal) Manufacturers Zhejiang Heyi APPLICATIONS: Mode of action Foliar fungicide with protective action. Uses Fungicidal control in fruit, vegetables, ornamentals, and feld crops. Particular uses included control of blossom blights, scab on apples and pears, and brown rot of stone fruit. Also used to control blue-green Algae in ponds, lakes, and swimming pools. Formulation types WP. Compatibility Incompatible with petroleum oils, dinitro compounds, organomercury compounds, calcium arsenate, lime sulfur, Bordeaux mixture, nicotine, and emulsifable concentrate formulations. PRODUCTS: Discontinued products ‘Kolo’* (FMC); ‘Phygon’* (Uniroyal). ANALYSIS: Product analysis by colorimetry after alkaline hydrolysis to the sodium salt of 2-chloro- 3-hydroxy-1,4-naphthoquinone (D. K. Gullstrom & H. P. Burchfeld, Anal. Chem., 1948, 20, 1174; J. R. Lane, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 3, 141). Residues O O Cl Cl 172 The Pesticide Manual Sixteenth Edition © BCPC 2012 dichlorfurenol; dichlorfurenol-methyl determined by glc (Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 584) or by colorimetry (AOAC Methods, 18th Ed., 965.36). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1300 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 5000 mg/kg. Irritating to skin under warm conditions. NOEL In 2 y feeding trials, rats receiving 1500 mg/kg diet showed no ill-effects. ADI/RfD (EPA) 0.08 mg/kg b.w. [1989]. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| Xi; R36/38| N; R50, R53 ECOTOXICOLOGY: Fish LC 50 (48 h) for brown trout 0.31 mg/l. Daphnia LC 50 0.014 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Plants In plant cells, both chlorine atoms are replaced by sulfhydryl groups to give a substituted dimercapto compound. dichloralurea Herbicide NOMENCLATURE: Common name DCU (WSSA); dichloralurea (BSI, E-ISO); dichloraluré(e) (F-ISO); are accepted in lieu of a common name IUPAC name 1,3-bis(2,2,2-trichloro-1-hydroxyethyl)urea Chemical Abstracts name N,N′-bis(2,2,2-trichloro-1-hydroxyethyl)urea CAS RN [116–52–9] Development codes Crag Herbicide 2 Smiles code OC(NC(=O)NC(O)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 354.8 M.f. C 5 H 6 Cl 6 N 2 O 3 COMMERCIALISATION: History Herbicide introduced by Union Carbide Corp. (later Rhône-Poulenc Ag.). PRODUCTS: Discontinued products ‘Crag Herbicide 2’* (Union Carbide). dichlorfurenol; dichlorfurenol-methyl Plant growth regulator NOMENCLATURE: Common name dichlorfurenol (BSI from 1990, E-ISO); dichlorofuré(nol) ((m) F-ISO); dichlorfurecol* (BSI until 1990, Canada) Supplementary Entries – Extended 1,3-dichloro-1,1,3,3-tetrafuoroacetone hydrate 173 IUPAC name 2,7-dichloro-9-hydroxyfuorene-9-carboxylic acid Chemical Abstracts name 2,7-dichloro-9-hydroxy-9H-fuorene-9-carboxylic acid CAS RN [21634–96–8] dichlorfurenol-methyl Development codes IT-5733 PHYSICAL CHEMISTRY: Composition Dichlorfurenol-methyl is present as a minor component of tech. chlorfurenol-methyl (q.v.). Mol. wt. 295.1; (methyl ester 309.2) M.f. C 14 H 8 Cl 2 O 3 ; (methyl ester C15H 10 Cl 2 O3) COMMERCIALISATION: History Dichlorfurenol-methyl introduced as a plant growth regulator by E. Merck (later Shell Agrar GmbH). dichlormate Herbicide NOMENCLATURE: Common name dichlormate (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name 3,4-dichlorobenzyl methylcarbamate Chemical Abstracts name (3,4-dichlorophenyl)methyl methylcarbamate CAS RN [1966–58–1] dichlormate; [62046–37–1] tech. grade containing 2,3-dichloro- analogue Development codes UC 22 463A (pure dichlormate); UC 22 463 (TC grade) Smiles code CNC(=O)OCc1ccc(Cl)c(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 234.1 M.f. C 9 H 9 Cl 2 NO 2 COMMERCIALISATION: History Herbicide reported by R. A. Herrett & R. V. Berthold (Science, 1965, 149, 191). Introduced by Union Carbide Corp. (later Rhône-Poulenc Ag.). PRODUCTS: Discontinued products ‘Rowmate’* (Union Carbide). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. 1,3-dichloro-1,1,3,3-tetrafuoroacetone hydrate Fungicide NOMENCLATURE: IUPAC name 1,3-dichloro-1,1,3,3-tetrafuoropropane-2,2-diol (i); 1,3-dichloro-1,1,3,3,- tetrafuoroacetone hydrate (ii) Chemical Abstracts name 1,3-dichloro-1,1,3,3-tetrafuoro-2,2-propanediol (i); 1,3-dichloro-1,1,3,3-tetrafuoro-2-propanone hydrate (ii) CAS RN [993–58–8] (i); [127–21–9] (ii) Development codes GC 9832 174 The Pesticide Manual Sixteenth Edition © BCPC 2012 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane PHYSICAL CHEMISTRY: Mol. wt. 216.9 M.f. C 3 H 2 Cl 2 F 4 O 2 COMMERCIALISATION: History Fungicide reported by D. W. George (Plant Dis. Rep., 1964, 48, 162). Introduced by Allied Chemical Corp. 1,1-dichloro-1-nitroethane Insecticide NOMENCLATURE: IUPAC name 1,1-dichloro-1-nitroethane (I) Chemical Abstracts name (I) CAS RN [594–72–9] Smiles code CC(Cl)(Cl)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 144.0 M.f. C 2 H 3 Cl 2 NO 2 COMMERCIALISATION: History Insecticidal activity reported by W. C. O’Kane & H. W. Smith (J. Econ. Entomol., 1941, 34, 438). Introduced by Commercial Solvents Corp. APPLICATIONS: Mode of action Fumigant insecticide. PRODUCTS: Discontinued products ‘Ethide’* (Commercial Solvents). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 410 mg/kg (Shibuya). EC Classifcation T; R23/24/25 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane Insecticide NOMENCLATURE: IUPAC name 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane Chemical Abstracts name 1,1′-(2,2-dichloroethylidene)bis[4-ethylbenzene] Other names ethylan CAS RN [72–56–0] Development codes Q-137 (Rohm & Haas); Bayer 63138 Smiles code CCc1ccc(cc1)C(C(Cl)Cl)c2ccc(CC)cc2 PHYSICAL CHEMISTRY: Mol. wt. 307.3 M.f. C 18 H 20 Cl 2 Form Crystalline solid; (tech. is a wax). M.p. 60–61 °C; (tech., ≥40 °C) Solubility Practically insoluble in water. Soluble in most aromatic solvents and in dichloromethane. COMMERCIALISATION: History Insecticide introduced by Rohm & Haas Co. Patents US 2464000, US 2881111, US 2883428. Supplementary Entries – Extended 2,4-dichlorophenyl benzenesulfonate 175 APPLICATIONS: Mode of action Non-systemic insecticide with useful specifcity. Uses For control of pear psylla, and use against leafhoppers and various larvae on vegetable crops, at 1–16 kg/ha. Also used domestically for the control of clothes moth and carpet beetles. PRODUCTS: Discontinued products ‘Perthane’* (Rohm & Haas). ANALYSIS: Residues determined by glc, tlc or paper chromatography (AOAC Methods 18th Ed., 970.52) or by glc with ECD of a dehydrochlorinated derivative (ibid., 973.39). See also Pestic. Anal. Man., I, 303, 304. ENVIRONMENTAL FATE: Soil/Environment Moderately persistent in soil. O-2,5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate Insecticide IRAC 1B NOMENCLATURE: IUPAC name O-2,5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate Chemical Abstracts name O-(2,5-dichloro-4-iodophenyl) O-ethyl ethylphosphonothioate CAS RN [25177–27–9] Development codes C 18 244 Smiles code CCOP(=S)(CC)Oc1cc(Cl)c(I)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 425.1 M.f. C 10 H 12 Cl 2 IO 2 PS COMMERCIALISATION: History Insecticide introduced by Ciba AG (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. 2,4-dichlorophenyl benzenesulfonate Acaricide NOMENCLATURE: IUPAC name 2,4-dichlorophenyl benzenesulfonate (I) Chemical Abstracts name (I) Other names DCPBS CAS RN [97–16–5] Development codes EM-923; GC-923 Smiles code Clc1ccc(OS(=O)(=O)c2ccccc2) c(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 303.2 M.f. C 12 H 8 Cl 2 O 3 S 176 The Pesticide Manual Sixteenth Edition © BCPC 2012 N-3,5-dichlorophenylsuccinimide COMMERCIALISATION: History Acaricide introduced by Allied Chemical Corp., Agrochemical Division (later Hopkins Agricultural Chemical Co.). PRODUCTS: Discontinued products ‘Genite’* (Allied); ‘Genitol’* (Allied). (RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)succinimide Fungicide NOMENCLATURE: IUPAC name (RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)succinimide Chemical Abstracts name (±)-1-(3,5-dichlorophenyl)-3-(methoxymethyl)-2,5- pyrrolidinedione Other names metomeclan* (unadopted proposed common name) CAS RN [81949–88–4] Development codes Co 6054 Smiles code COCC1CC(=O)N(C1=O)c2cc(Cl)cc(Cl)c2 PHYSICAL CHEMISTRY: Mol. wt. 288.1 M.f. C 12 H 11 Cl 2 NO 3 COMMERCIALISATION: History Fungicide evaluated by Wacker-Chemie GmbH. PRODUCTS: Discontinued products ‘Drawifol’* (Wacker). N-3,5-dichlorophenylsuccinimide Fungicide NOMENCLATURE: IUPAC name N-3,5-dichlorophenylsuccinimide Chemical Abstracts name 1-(3,5-dichlorophenyl)-2,5-pyrrolidinedione CAS RN [24096–53–5] Development codes S-47127 Smiles code Clc1cc(Cl)cc(c1)N 2 C(=O)CCC2=O PHYSICAL CHEMISTRY: Mol. wt. 244.1 M.f. C 10 H 7 Cl 2 NO 2 COMMERCIALISATION: History Fungicide introduced by Sumitomo Chemical Co., Ltd. PRODUCTS: Discontinued products ‘Ohric’* (Sumitomo Chemical). Supplementary Entries – Extended 1,2-dichloropropane with 1,3-dichloropropene 177 1,2-dichloropropane Insecticide NOMENCLATURE: IUPAC name 1,2-dichloropropane (I) Chemical Abstracts name (I) Other names propylene dichloride; PDC CAS RN [78–87–5] EC no 201–152–2 Smiles code CC(Cl)CCl PHYSICAL CHEMISTRY: Mol. wt. 113.0 M.f. C 3 H 6 Cl 2 Form Colourless liquid. M.p. Freezes –70 °C B.p. 95.4 °C V.p. 2.79 × 107 mPa (19.6 °C) K ow logP = 2.28 (Agchem. Desk Ref.) Henry 1.17 × 103 Pa m 3 mol –1 (calc.) S.g./density 1.1595 (20 °C) Solubility In water 2.7 g/kg (20 °C). Miscible with ethanol, diethyl ether. Stability Stable at pH 7 (25 °C) (Agchem. Desk Ref.) F.p. 21 °C (Cleveland open cup) COMMERCIALISATION: History Its properties as an insecticidal fungicide were described by I. E. Neifert et al. (U.S. Dep. Agric. Bull., 1925, No. 1313). APPLICATIONS: Mode of action Fumigant insecticide. Uses Used in mixture with 1,3-dichloropropene. Although far less toxic to nematodes (C. R. Youngston & C. I. A. Goring, Plant Dis. Rep., 1970, 54, 196; M. V. McKenry & I. J. Thomason, Hilgardia, 1974, 42, 422) it moves more freely in soil, from which the greatest loss is by volatilisation (T. R. Roberts & G. Stoydin, Pestic. Sci., 1976, 7, 325). ANALYSIS: Product and residue analysis is by glc. Methods reviewed by J L Daft in Comp. Anal. Profles,Chapter 11. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 146 (1993). HSG 76 (1992). IARC 41 (1986); 71 (1999). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: IARC Class 3 Inhalation It is strongly narcotic but low concentrations cause an irritation of the respiratory tract. Exposure of guinea-pigs, rabbits and rats to the vapour has been studied (L. A. Heppel et al., J. Ind. Hyg. Toxicol., 1946, 28, 1). Water GV 0.04 mg/l (provisional). Toxicity Class WHO (a.i.) FM EC Classifcation F; R11| Xn; R20/22 1,2-dichloropropane with 1,3-dichloropropene Insecticide, nematicide NOMENCLATURE: IUPAC name 1,2-dichloropropane + 1,3-dichloropropene Chemical Abstracts name 1,2-dichloropropane + 1,3-dichloro-1-propene 178 The Pesticide Manual Sixteenth Edition © BCPC 2012 1,2-dichloropropane with 1,3-dichloropropene CAS RN [8003–19–8] mixture; [78–87–5] 1,2-dichloropropane; [542–75– 6] 1,3-dichloropropene Smiles code CC(Cl)CCl.ClC/C=C/Cl;without stereochemistry:CC(Cl)CCl.ClCC=CCl PHYSICAL CHEMISTRY: Composition A mixture of chlorinated hydrocarbons containing ≥50% m/m (E)- and (Z)-1,3-dichloropropenes, the other main constituent being 1,2-dichloropropane. It has an organic chlorine content of ≥55.0% m/m. Form Clear amber liquid, with a pungent odour. B.p. Flash distils 59–115 °C V.p. 4.6 × 10{6} mPa (20 °C) S.g./density 1.17–1.22 (20 °C) Solubility In water c. 2 g/kg (room temperature). Fully miscible with esters, halogenated solvents, hydrocarbons and ketones. Stability The mixture is stable at ≤500 °C but reacts with dilute organic bases, concentrated acids, halogens and some metal salts. F.p. 17.5 °C (Abel closed cup) COMMERCIALISATION: History Properties as a soil fumigant described by W. Carter (Science, 1943, 97, 383). Introduced by Shell Chemical Co. and by Dow Chemical Co., later replaced by 1,3-dichloropropene. APPLICATIONS: Mode of action Fumigant insecticide and nematicide. Uses The mixture is a pre-plant nematicide effective against soil nematodes including root knot, meadow, sting and dagger, spiral and sugar beet nematodes. Because the components are highly phytotoxic, a 7-d pre- planting interval was allowed for every 75 l applied/ha. PRODUCTS: Discontinued products ‘DD’* (Shell); ‘Vidden D’* (Dow). ANALYSIS: Product and residue analysis is by glc (T. R. Roberts & G. Stoydin, Pestic. Sci., 1976, 7, 325; C. E. Castro, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 3, 151; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 710). Methods reviewed by J L Daft in Comp. Anal. Profles,Chapter 11. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 146 (1993). HSG 76 (1992). EFSA Sci. Rep. (2006) 72, 1–99. IARC 41 (1986); 71 (1999). EU Status (1107/2009) 1,3-dichloropropene not included, 2007/619/EC. 1,2-dichloropropane and the (Z)-isomer of 1,3-dichloropropene not included, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 132–227, mice 314 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 779, rabbits 2100 mg/kg. Extremely irritating to the skin and a severe eye irritant. Also a moderate skin sensitiser. NOEL In 2 y feeding trials, no effects related to the product were observed in rats receiving ≤120 mg product/kg diet. Water GV See individual data for the components. Supplementary Entries – Extended 2,2-dichlorovinyl 2-ethylsulfnylethyl methyl phosphate 179 ENVIRONMENTAL FATE: Soil/Environment It does not accumulate in the soil (M. V. McKenry & I. J. Thomason, Hilgardia, 1974, 42, 393; T. R. Roberts & G. Stoydin, Pestic. Sci., 1976, 7, 325); and has no permanent harmful effect on soil micro-organisms. 3,4-dichlorotetrahydrothiophene 1,1-dioxide Nematicide NOMENCLATURE: IUPAC name 3,4-dichlorotetrahydrothiophene 1,1-dioxide (I) Chemical Abstracts name (I) Other names dichlorothiolane dioxide CAS RN [3001–57–8] Smiles code ClC1CS(=O)(=O)CC1Cl PHYSICAL CHEMISTRY: Mol. wt. 189.1 M.f. C 4 H 6 Cl 2 O 2 S COMMERCIALISATION: History Nematicide introduced by Diamond Shamrock Chemical Co. (later Fermenta). PRODUCTS: Discontinued products ‘PRD Experimental Nematicide’* (Fermenta). 2,2-dichlorovinyl 2-ethylsulfnylethyl methyl phosphate Insecticide IRAC 1B NOMENCLATURE: IUPAC name 2,2-dichlorovinyl 2-ethylsulfnylethyl methyl phosphate Chemical Abstracts name 2,2-dichloroethenyl 2-(ethylsulfnyl)ethyl methyl phosphate CAS RN [7076–53–1] Development codes Nexion 1378 Smiles code CCS(=O) CCOP(=O)(OC)OC=C(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 311.1 M.f. C 7 H 13 Cl 2 O 5 PS COMMERCIALISATION: History Insecticide introduced by Celamerck GmbH & Co. (later Shell Agrar GmbH). APPLICATIONS: Biochemistry Cholinesterase inhibitor. MAMMALIAN TOXICOLOGY: EC Classifcation T; R23/24/25 180 The Pesticide Manual Sixteenth Edition © BCPC 2012 diclobutrazol dichlozoline Fungicide NOMENCLATURE: Common name dichlozoline (BSI, E-ISO, (f) F-ISO, JMAF, ex ANSI) IUPAC name 3-(3,5-dichlorophenyl)-5,5-dimethyl-1,3-oxazolidine-2,4-dione Chemical Abstracts name 3-(3,5-dichlorophenyl)-5,5-dimethyl-2,4-oxazolidinedione Other names DDOD CAS RN [24201–58–9] Development codes CS 8890; Ortho 8890 Smiles code CC1(C)OC(=O)N(C1=O)c2ccc(Cl)c(Cl)c2 PHYSICAL CHEMISTRY: Mol. wt. 274.1 M.f. C 11 H 9 Cl 2 NO 3 COMMERCIALISATION: History Fungicide evaluated by Chevron Chemical Company LLC. PRODUCTS: Discontinued products ‘Sclex’* (Sumitomo Chemical). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O diclobutrazol Fungicide NOMENCLATURE: Common name diclobutrazol (BSI, E-ISO, (m) F-ISO) IUPAC name (2RS,3RS)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl) pentan-3-ol Chemical Abstracts name (R*,R*)-(±)-β-[(2,4-dichlorophenyl)methyl]-α-(1,1- dimethylethyl)-1H-1,2,4-triazole-1-ethanol CAS RN [75736–33–3] diclobutrazol; [66345–62–8] unstated stereochemistry EC no 266–324–1 unstated stereochemistry Development codes PP296 Smiles code CC(C)(C)C(O)C(Cc1ccc(Cl)cc1Cl)n2cncn2 PHYSICAL CHEMISTRY: Mol. wt. 328.2 M.f. C 15 H 19 Cl 2 N 3 O Form Off-white crystalline solid. M.p. 147–149 °C V.p. 0.0027 mPa (20 °C) K ow logP = 3.81 Henry 1.25 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.25 Solubility In water 7.1 mg/l H C OH CH N N N C(CH 3 ) 3 CH 2 Cl Cl Supplementary Entries – Extended diclobutrazol 181 (pH 7, room temperature). In acetone, methanol, ethanol, chloroform <50 g/l. Moderately soluble in DMF, cyclohexanone, monobutyl ether, and glycol ethers. Slightly soluble in xylene. Stability Stable to acids and alkalis (pH 4–14). Also stable to heat (>90 d, 50 °C), air, sunlight, and moisture. pKa Basic, pKa <2 COMMERCIALISATION: History Fungicide reported by K. J. Bent & A. M. Skidmore (Proc. Br. Crop Prot. Conf. - Pests Dis., 1979, 2, 477). Introduced by ICI Agrochemicals (became Syngenta AG). Patents GB 1595698 APPLICATIONS: Biochemistry Sterol demethylation (ergosterol biosynthesis) inhibitor. Mode of action Systemic fungicide with curative and protective action. Translocated within the plant predominantly acropetally. Also exhibits vapour action. Uses Control of rusts on cereals and coffee; and powdery mildews on cereals, vines, apples, and cucurbits. Phytotoxicity Should not be used on solanaceous crops. Formulation types SC. PRODUCTS: Discontinued products ‘Vigil’* (Zeneca); Discontinued mixtures ‘Sopraphal’* (+ prochloraz) (Syngenta). ANALYSIS: Residues in crops determined by glc with ECD (Pestic. Anal. Man., I, 302). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 4000, mice >1000, guinea pigs 4000, rabbits 4000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and rabbits >1000 mg/kg. Mild skin and eye irritant (rabbits). Not a skin sensitiser. NOEL (90 d) for rats 2.5 mg/kg daily; (6 mo) for dogs 15 mg/kg daily. Other Acute i.p. LD 50 for ratsc. 500 mg/kg. Toxicity Class WHO (a.i.) U EC Classifcation Xi; R36| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks >9461 mg/kg. Fish LC 50 (24 h) for rainbow trout 23.9 mg/l, (48 h) 15.1 mg/l, (96 h) 9.6 mg/l. Daphnia LC 50 (48 h) 9.3 mg/l. Bees LD 50 (oral and contact) 0.05 mg/bee. Worms No adverse effect on earthworm populations 30–245 d after application of sprays at 0.2 and 2.0 kg/ha. Other benefcial No adverse effect on soil microarthropods 30–245 d after application of sprays at 0.2 and 2.0 kg/ha. ENVIRONMENTAL FATE: Soil/Environment In straw, DT 50 c. 1 week. 182 The Pesticide Manual Sixteenth Edition © BCPC 2012 diclomezine diclomezine Fungicide FRAC 37, U; pyridazinone fungicide NOMENCLATURE: Common name diclomé(zine) ((f) F-ISO); diclomezine (BSI, E-ISO) IUPAC name 6-(3,5-dichloro-4-methylphenyl)pyridazin-3(2H)-one Chemical Abstracts name 6-(3,5-dichloro-4-methylphenyl)-3(2H)-pyridazinone CAS RN [62865–36–5] Development codes F-850 (Sankyo); SF-7531 (Sankyo) Smiles code Cc1c(Cl)cc(cc1Cl)c2ccc(=O)[nH]n2 PHYSICAL CHEMISTRY: Mol. wt. 255.1 M.f. C 11 H 8 Cl 2 N 2 O Form Colourless crystals. M.p. 250.5–253.5 °C V.p. <1.3 × 10-2 mPa (60 °C) Solubility In water 0.74 mg/l (25 °C). In methanol 2.0, acetone 3.4 (both in g/l, 23 °C). Stability Slowly decomposed by sunlight. Stable under acidic, neutral, and alkaline conditions. COMMERCIALISATION: History Fungicide reported by Y. Takahi (Jpn. Pestic. Inf., 1988, No. 52, p. 31). Introduced in Japan (1988) by Sankyo Co., Ltd (agrochemicals interests now Mitsui Chemicals Inc.). Patents US 4052395; GB 1533010; JP 1170243 Manufacturers Mitsui Chemicals Agro; Sankyo Agro APPLICATIONS: Mode of action Fungicide with curative and protective action. Inhibits septum formation and mycelial growth. Uses Control of Rhizoctonia and Sclerotium spp. in rice; white mould and twig rot on peanuts; and Rhizoctonia disease of turf. Applied at 360–480 g/ha. Formulation types DP; SC. WP. PRODUCTS: Other mixtures ‘Rabu-Monguard-Jorker’ (+ phthalide + silafuofen) (Hokko); Discontinued products ‘Monguard’* (Sankyo Agro). ANALYSIS: Product analysis by hplc. Residues determined by glc of a derivative. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >12 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Not a skin irritant. Inhalation LC 50 (4 h) for rats 0.82 mg/l. NOEL (2 y) for male rats 98.9, female rats 99.5 mg/kg daily. Other Non-mutagenic and non-teratogenic. Toxicity Class WHO (a.i.) U. CH 3 Cl Cl N N O H Supplementary Entries – Extended dicyclonon 183 ECOTOXICOLOGY: Birds Dietary LC 50 for bobwhite quail and mallard ducks >7000 ppm. Dietary LD 50 for bobwhite quail >3000 mg/kg. Fish LC 50 (48 h) for carp >300 mg/l. Daphnia LC 50 (5 h) >300 mg/l. Bees LD 50 (oral and contact) for honeybees >100 μg/bee. ENVIRONMENTAL FATE: Soil/Environment Readily adsorbed on soil particles. dicyclonon Herbicide safener NOMENCLATURE: Common name dicyclonone ((f) F-ISO); dicyclonon (BSI, E-ISO) IUPAC name (RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6- one Chemical Abstracts name 1-(dichloroacetyl)hexahydro-3,3,8a-trimethylpyrrolo[1,2-a] pyrimidin-6(2H)-one CAS RN [79260–71–2]; [110499–25–7] (R)- isomer; [110499–27–9] (S)- isomer; the substance named dicyclonon in Chemical Abstracts Registry, with Registry Number [85072–82–8], is actually an isomer of dicyclonon, with a methyl group in position 7 instead of at the bridgehead position 8a. Development codes BAS 145138 (BASF) PHYSICAL CHEMISTRY: Mol. wt. 293.2 M.f. C 12 H 18 Cl 2 N 2 O 2 COMMERCIALISATION: Manufacturers BASF APPLICATIONS: Biochemistry Enhances cytochrome P450-mediated oxidative metabolism of the herbicide, and its subsequent conjugation (see J. Davies & J. C. Caseley, Pestic. Sci. 1999, 55(11) 1043–1058). Uses Can be used to safen maize to a wide variety of herbicides. (RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one N N O O Cl Cl (RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one Caution: Stereochemical terms discarded: s 184 The Pesticide Manual Sixteenth Edition © BCPC 2012 dicyclopentadiene dicyclopentadiene Animal repellent NOMENCLATURE: IUPAC name 3a,4,7,7a-tetrahydro-1H-4,7-methano-indene Chemical Abstracts name 3a,4,7,7a-tetrahydro-4,7-methano-1H-indene CAS RN [77– 73–6] Smiles code C1C=CC2C3CC(C=C3)C 12 PHYSICAL CHEMISTRY: Mol. wt. 132.2 M.f. C 10 H 12 Form Colourless crystals. M.p. 32.7 °C B.p. 64.5 °C /14 mm Hg V.p. 0.33 mPa (25 °C) S.g./density 0.9766 (33 °C) Solubility Sparingly soluble in water. Readily soluble in acetone, dichloromethane, ethyl acetate, hexane, and toluene. Stability Chemically very stable. COMMERCIALISATION: History Animal repellent introduced by Staehler. APPLICATIONS: Uses As a repellent for animals such as hares, rabbits, and deer, in winter or in summer. Applied in the form of impregnated strips on deciduous and coniferous trees, or by spraying around ornamental plants and shrubs. Normally used in combination with other materials. Formulation types SC. ANALYSIS: Product by glc with FID. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.873 (2005). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 750 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 6720 mg/kg. Mild skin and eye irritant (rabbits). Inhalation LC 50 (4 h) for rats 660 mg/l air. ECOTOXICOLOGY: Fish LC 50 (96 h) for carp 62.2, rainbow trout 22.86 mg/l. Bees Not toxic to bees. Supplementary Entries – Extended dieldrin 185 dieldrin Insecticide IRAC 2A NOMENCLATURE: Common name HEOD (for pure compound) (BSI, E-ISO, F-ISO, JMAF); dieldrine ((f) F-ISO); dieldrin (USSR before 1984, Denmark); dieldrin (material containing >85% HEOD) (BSI, E-ISO, BAN, ESA, JMAF, except Denmark) IUPAC name (1R,4S,4aS,5R,6R,7S,8S,8aR)-1,2,3,4,10,10-hexachloro-1,4,4a,5,6,7,8,8a- octahydro-6,7-epoxy-1,4:5,8-dimethanonaphthalene Chemical Abstracts name (1aα,2β,2aα,3β,6β,6aα,7β,7aα)-3,4,5,6,9,9-hexachloro- 1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-dimethanonaphth[2,3-b]oxirene CAS RN [60–57–1] EC no 200–484–5 Development codes Compound 497 (to Hyman) Smiles code ClC1=C(Cl)C2(Cl)C3C4CC(C5OC54)C3C1(Cl)C2(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 380.9 M.f. C 12 H 8 Cl 6 O Form Tech. consists of buff to light tan fakes with a mild odour. M.p. 175–176 °C; (tech. sets at >95 °C) V.p. 0.4 mPa (20 °C) Henry 8.19 × 10 –1 Pa m 3 mol –1 (calc.) S.g./density 1.62 (20 °C) Solubility In water 0.186 mg/l (20 °C). Stability Stable to alkali, mild acids and to light. It reacts with concentrated mineral acids, acid catalysts, acid oxidising agents and active metals (iron, copper). COMMERCIALISATION: History Insecticide reported by C. W. Kearns et al. (J. Econ. Entomol., 1949, 42, 127). Introduced by J. Hyman & Co. and later by the Shell International Chemical Co., Ltd. Patents US 2676547 APPLICATIONS: Biochemistry Antagonist of the GABA receptor-chloride channel complex. Mode of action Contact and ingested insecticide. Uses A presistent insecticide, used to control locusts and tropical disease vectors, such as Glossina spp. Industrial uses included timber preservation, termite-proofng of plastic and rubber coverings of electrical and telecommunication cables, of plywood and building boards and as a termite barrier in building construction. Formulation types EC; GR; WP. PRODUCTS: Discontinued products ‘Octalox’* (Hyman). ANALYSIS: Product analysis by glc, by i.r. spectrophotometry (CIPAC Handbook, 1983, 1B, 1780; FAO Specifcation (CP/36), Organochlorine Insecticides 1973; AOAC Methods 18th Ed., 961.05), by tlc (ibid., 972.05), or by potentiometric titration of liberated chloride ion (CIPAC Handbook, 1994, F, 190). Residues determined by glc, tlc or paper chromatography (AOAC Methods, 18th Ed., 970.52; ibid., 985.22), or by glc with ECD (Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 268; Analyst (London), 1979, 104, 425; P. A. Greve & W. B. F. 186 The Pesticide Manual Sixteenth Edition © BCPC 2012 dienochlor Grevenstuk, Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1975, 40, 1115; G. M. Telling et al., J. Chromatogr., 1977, 137, 405; M. A. Luke et al., J. Assoc. Off. Anal. Chem., 1981, 64, 1187; ibid., 1985, 68, 385, 29.A01–29.A04). See also Pestic. Anal. Man., I, 204, 208, 301, 302, 303, 304, 402, 502. In drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 91 (1989). JMPR Mtg. 65 (1992); JMPR Evaln. 29 (1977). HSG 21 (1989). PDS 17 (1975). ICSC.787 (1998). IARC 5 (1974); Suppl. 7 (1987). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EC, as amended by Regulation 850/2004. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for rats 37–87, rabbits 45–50 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 60–90 mg/kg. NOEL In long-term exposure, NOEL for rats and dogs 0.1 mg/kg diet (0.005 mg/kg daily). Data available indicate that dieldrin and aldrin do not produce malignant tumours in rats, dogs, monkeys at all tolerated dose levels in long-term feeding studies. The signifcance of the marginal increase in incidence of hepatic tumours in mice, following lifetime exposure to dieldrin, is doubtful. ADI/RfD (JMPR) 0.0001 mg (total aldrin + dieldrin)/kg b. w. (PTDI) [1994]; (EPA) cRfD 0.00005 mg/kg b.w. [1990]. Water GV 0.03 μ;g/l (sum of aldrin+dieldrin). Toxicity Class WHO (a.i.) Ib EC Classifcation T+; R27| T; R25, R48/25| R40| N; R50, R53 PIC Yes. ENVIRONMENTAL FATE: Animals Oxidised in the liver to a hydrophilic hydroxy compound, and is subsequently eliminated in the urine as the glucuronic acid conjugate. dienochlor Acaricide NOMENCLATURE: Common name dienochlor (BSI, E-ISO); dié(nochlore) ((m) F-ISO) IUPAC name perchloro-1,1′-bicyclopenta-2,4-diene Chemical Abstracts name 1,1′,2,2′,3,3′,4,4′,5,5′-decachlorobi-2,4-cyclopentadien-1-yl CAS RN [2227–17–0] Development codes SAN 804 I Smiles code ClC1=C(Cl)C(Cl) (C(=C1Cl)Cl)C2(Cl)C(=C(Cl)C(=C2Cl)Cl)Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Supplementary Entries – Extended dienochlor 187 PHYSICAL CHEMISTRY: Mol. wt. 474.6 M.f. C 10 Cl 10 Form Grey crystals; (tech., light yellow powder, sometimes with faint onion or garlic odour). M.p. 122–123 °C; (tech., 111–128 °C) B.p. 250 °C (decomp.) V.p. 0.29 mPa (extrapolated to 25 °C) K ow logP = 3.23 (mean, 25 °C) S.g./density 1.923 (tech., 25 °C) Solubility Practically insoluble in water (25 ppb). In iso-octane 7.89, toluene 59.00, acetonitrile 1.16, n-octanol 4.77, tetrahydrofuran 98.32 (all in g tech./100 ml). Stability Tech. dienochlor was stable when stored at 54 °C for 14 d, and at 42 °C for 2 y. Hydrolysis DT 50 (25 °C) 30.5 d (pH 9), 93 d (pH 7), 184 d (pH 5). DT 50 as thin flm solution in simulated sunlight 1.6 min. COMMERCIALISATION: History Acaricide reported by W. W. Allen et al. (J. Econ. Entomol., 1964, 57, 187). Introduced by Hooker Chemical Corp. and later by Zoecon Corp., followed by Sandoz AG (later Novartis Crop Protection AG). Patents US 2732409; US 2934470 (to Hooker) Manufacturers Novartis APPLICATIONS: Mode of action Acaricide with predominantly contact action. Interferes with oviposition. Long residual activity under glasshouse conditions. Uses Control of mites (Tetranychus spp., Panonychus ulmi, and Polyphagotarsonemus latus) on roses, chrysanthemums, and other ornamentals, normally under glass. Formulation types WP; EW . PRODUCTS: Discontinued products ‘Pentac’* (Novartis); ‘Pentac Aquafow’* (Dow). ANALYSIS: Product analysis by hplc spectroscopy. Residues determined by hplc. In soil, by gc/ECD (Environ. Chem. Methods). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male albino rats >3160 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rabbits >3160, rats >2000 mg/kg. Mildly irritating to eyes and skin (rabbits). Sensitising to skin. Inhalation LC 50 (4 h) for rats 0.08 mg/l air. Toxicity Class WHO (a.i.) III EPA (formulation) I ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 4319 mg/kg. Dietary LC 50 (8 d) for mallard ducks 3966, bobwhite quail >5620 mg/kg diet. Fish LC 50 (96 h) for rainbow trout 0.050, bluegill sunfsh 0.6 mg/l. Daphnia LC 50 (48 h) 1.2 mg/l. Algae NOEC (96 h) for Scenedesmus subspicatus >30 mg/l. Bees LD 50 (contact) >36 μg/bee. Worms LC 50 (7d and 14 d) >1000 mg/kg dry soil. ENVIRONMENTAL FATE: Animals Rapid degradation was observed in rats. Within 4 days, following a single oral dose of 1 mg/kg, female rats excreted 2% and 88% of applied 14C in urine and faeces 188 The Pesticide Manual Sixteenth Edition © BCPC 2012 diethatyl-ethyl; diethatyl respectively. Plants Major degradation products are perchloroketones. Degradation is mainly photochemical rather than metabolic; DT 50 2–3 d when plants are exposed to sunlight. Soil/Environment Soil adsorption Kd 384 (silty loam, pH 6.1, 3.6% o.m.), 196 (loamy sand, pH 7.5, 0.5% o.m.), 269 (silty clay loam, pH 6.8, 11.8% o.m.), 311 (sandy loam, pH 6.9, 1.3% o.m.). In soil DT 50 3.1 d. diethamquat; diethamquat dichloride Herbicide NOMENCLATURE: Common name diethamquat (BSI, E-ISO, (m) F-ISO) IUPAC name 1,1′-bis(diethylcarbamoylmethyl)-4,4′-bipyridinium Chemical Abstracts name 1,1′-bis[2-(diethylamino)-2-oxoethyl]-4,4′-bipyridinium CAS RN [4029–02–1] dichloride, formerly [111156–45–7]; [400852–67–7] dication Development codes PP831 PHYSICAL CHEMISTRY: Mol. wt. 384.5; (diethamquat dichloride 455.4) M.f. C 22 H 32 N 4 O 2 ; (diethamquat dichloride C22H32Cl 2 N4O 2 ) COMMERCIALISATION: History Dichloride evaluated as herbicide by ICI Plant Protection Division (later ICI Agrochemicals). diethatyl-ethyl; diethatyl Herbicide NOMENCLATURE: Common name (for the acid) diethatyl (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name (acid) N-chloroacetyl-N-(2,6-diethylphenyl)glycine Chemical Abstracts name (acid) N-(chloroacetyl)-N-(2,6-diethylphenyl)glycine CAS RN [38727–55–8] ethyl ester; [38725–95–0] acid Development codes (acid) Hercules 22 234 Smiles code acid:CCc1cccc(CC)c1N(CC(=O)O)C(=O) CCl;ester:CCOC(=O)CN(C(=O)CCl)c1c(CC)cccc1CC PHYSICAL CHEMISTRY: Mol. wt. 311.8; (acid 283.8) M.f. C 16 H 22 ClNO 3 (ester); C 14 H18ClNO3 (acid) Form Colourless crystals. M.p. 49–50 °C V.p. 0.43 mPa (30 °C) K ow logP = 3.599 (pH 6.6, 25 °C) S.g./density 1.38 (25 °C) Solubility In water 105 mg/l (25 °C). In methanol, ethanol 810, isopropanol 750, acetone, xylene 820, methyl isobutyl ketone 830, chloroform 770, kerosene 200 (all in g/kg, room temperature). Stability Hydrolysed under strongly acidic or alkaline conditions. Thermally stable up to 240 °C. Tech. and formulations are stable for >2 y under normal conditions. Supplementary Entries – Extended diethatyl-ethyl; diethatyl 189 COMMERCIALISATION: History Herbicidal activity of the ethyl ester reported by S. K. Lehman (Proc. North Cent. Weed Control Conf., 29th, 1972); introduced by Hercules Inc. Agrochemicals (later Nor-Am Chemical Co.). Manufacturers NOR-AM APPLICATIONS: Biochemistry Inhibits cell division by blocking protein synthesis. It is reported that chloroacetamides inhibit synthesis of very long chain fatty acids (J. Schmalfuss et al., Abstr. Meeting WSSA, Toronto, 40, 117–118, 2000; P. Böger, Abstr. III Int. Weed Control Congr., Brazil, 2000). Mode of action Selective soil-herbicide, absorbed primarily by the emerging shoots, and secondarily by the roots. Uses Pre-plant soil-incorporated or pre-emergence control of annual grasses and some broad-leaved weeds in sugar beet, soya Beans, cotton, sunfowers, potatoes, peanuts, phaseolus beans, fodder beet, beetroot, sugar cane, fax, spinach, wheat, rice, and other crops at rates in the range 2.2–6.7 kg/ha. Formulation types EC. PRODUCTS: Discontinued products ‘Antor’* (diethatyl-ethyl) (AgrEvo). ANALYSIS: Product analysis by glc or hplc. Residues determined by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 2318, female rats 3720, male mice 1653, female mice 4118 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >4000 mg/kg. Mild skin and eye irritant (rabbits). NOEL (2 y) for rats and mice 1000 mg/kg diet, for dogs 50 mg/kg diet. In 3-generation study, NOEL for rats 200 mg/kg diet. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Diethatyl-ethyl: acute oral LD 50 for mallard ducks and bobwhite quail >10 000 mg/ kg. Fish LC 50 (24 h) for bluegill 7.14 mg/l (NOEL 2.4 mg/l), for rainbow trout 10.3 mg/l (NOEL 1.0 mg/l). LC 50 (96 h) for bluegill sunfsh 3.34, rainbow trout 1.82 mg/l. Bees Not toxic to bees at 43.5 μg/bee. ENVIRONMENTAL FATE: Plants In plants, diethatyl is rapidly metabolised (almost completely within 4 days), with translocation of metabolites throughout the plant. Soil/Environment In soil, micro- organisms appear to play a signifcant role in degradation. Residual activity persists for c. 6–10 weeks. 190 The Pesticide Manual Sixteenth Edition © BCPC 2012 diethyl 5-methylpyrazol-3-yl phosphate dietholate Herbicide safener NOMENCLATURE: Common name dietholate (WSSA) IUPAC name O,O-diethyl O-phenyl phosphorothioate (I) Chemical Abstracts name (I) CAS RN [32345–29–2] Development codes R 33865 PHYSICAL CHEMISTRY: Mol. wt. 246.3 M.f. C 10 H 15 O 3 PS APPLICATIONS: Biochemistry Appears to act by inhibiting metabolism of the carbonyl linkage of EPTC (T. B. Moorman et al., Soil Biol. Biochem., 1992, 24(2) 121). Uses Inhibits degradation of thiocarbamate herbicides, in soils with high microbial activity. Also acts as an insecticide synergist. (R. M. Hollingworth et al., Pure & Appl. Chem., 1995, 67, 1487–1532). PRODUCTS: Discontinued mixtures ‘Eradicane Extra’* (+ dichlormid + EPTC) (Zeneca). O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate Insecticide IRAC 1B NOMENCLATURE: IUPAC name O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate Chemical Abstracts name O,O-diethyl O-(6-methyl-2-propyl-4-pyrimidinyl) phosphorothioate CAS RN [5826–91–5] Development codes G 24 622 Smiles code CCCc1nc(C)cc(OP(=S)(OCC)OCC)n1 PHYSICAL CHEMISTRY: Mol. wt. 304.4 M.f. C 12 H 21 N 2 O 3 PS COMMERCIALISATION: History Insecticide introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Pyrazinon’* (Ciba-Geigy). diethyl 5-methylpyrazol-3-yl phosphate Insecticide IRAC 1B NOMENCLATURE: IUPAC name diethyl 5-methylpyrazol-3-yl phosphate Supplementary Entries – Extended O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate 191 Chemical Abstracts name diethyl 5-methyl-1H-pyrazol-3-yl phosphate Other names pyrazoxon CAS RN [108–34–9] Development codes G 24 483 Smiles code CCOP(=O)(OCC)Oc1cc(C)[nH]n1 PHYSICAL CHEMISTRY: Mol. wt. 234.2 M.f. C 8 H 15 N 2 O 4 P COMMERCIALISATION: History Insecticide introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Pyrazoxon’* (Ciba-Geigy). MAMMALIAN TOXICOLOGY: EC Classifcation T+; R26/27/28 O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate Insecticide IRAC 1B NOMENCLATURE: IUPAC name O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate; O,O- diethyl O-4-methylcoumarin-7-yl phosporothioate; 7-diethoxyphosphinothioyloxy-4- methylcoumarin Chemical Abstracts name O,O-diethyl O-(4-methyl-2-oxo-2H-1-benzopyran-7- yl) phosphorothioate CAS RN [299–45–6] Development codes E 838 (Bayer) Smiles code CCOP(=S)(OCC)Oc1ccc2c(C)cc(=O)oc2c1 PHYSICAL CHEMISTRY: Mol. wt. 328.3 M.f. C 14 H 17 O 5 PS COMMERCIALISATION: History Insecticide reported by G. Schrader (Angew. Chem., 1952, Monogr. No. 62, 2nd Ed.). Introduced by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Ingested insecticide. Uses For use against colorado beetle. PRODUCTS: Discontinued products ‘Potasan’* (Bayer); Discontinued mixtures ‘Potasan G’* (+ gamma-HCH) (Bayer). MAMMALIAN TOXICOLOGY: EC Classifcation T+; R26/27/28| N; R50, R53| concn. dep. 192 The Pesticide Manual Sixteenth Edition © BCPC 2012 difenoxuron difenopenten; difenopenten-ethyl Herbicide NOMENCLATURE: Common name difé(nopentè) ((m) F-ISO); difenopenten (BSI, E-ISO, ANSI, WSSA) IUPAC name (E)-(±)-4-[4-(α,α,α-trifuoro-p-tolyloxy)phenoxy]pent-2-enoic acid Chemical Abstracts name (E)-(±)-4-[4-[4-(trifuoromethyl)phenoxy]phenoxy]-2- pentenoic acid CAS RN [81416–44–6] difenopenten; [71101–05–8] difenopenten-ethyl Development codes XE-773; KK-80 (both for difenopenten-ethyl) PHYSICAL CHEMISTRY: Mol. wt. 352.3; (ethyl ester 380.4) M.f. C 18 H 15 F 3 O 4 ; (ethyl ester C20H19F3O4) COMMERCIALISATION: History Herbicide evaluated by Chevron Chemical Company LLC. difenoxuron Herbicide NOMENCLATURE: Common name difenoxuron (BSI, E-ISO, (m) F-ISO) IUPAC name 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea Chemical Abstracts name N′-[4-(4-methoxyphenoxy)phenyl]-N,N- dimethylurea CAS RN [14214–32–5] Development codes C 3470 Smiles code COc1ccc(Oc2ccc(NC(=O)N(C)C)cc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 286.3 M.f. C 16 H 18 N 2 O 3 Form Colourless crystals. M.p. 138–139 °C V.p. 1.24 × 10 –6 mPa (20 °C) Henry 1.78 × 10-8 Pa m 3 mol –1 (calc.) S.g./density 1.30 (20 °C) Solubility In water 20 mg/l (20 °C). In dichloromethane 156, acetone 63, isopropanol 10, benzene 8, hexane 0.05 (all in g/kg, 20 °C). Stability No signifcant hydrolysis occurs at 30 °C and pH 1 or 13. COMMERCIALISATION: History Herbicide reported by L. Ebner & J. Schuler (Proc. Br. Weed Control Conf., 7th, 1964, 2, 711). Introduced by Ciba-Geigy AG. Patents BE 593743; GB 913383 APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective herbicide, absorbed by the leaves and roots. Uses Control O NHCON(CH 3 ) 2 CH 3 O Supplementary Entries – Extended dihydroazadirachtin 193 of annual broad-leaved weeds post-emergence in onions, leeks, garlic, and other alliums at 2.5 kg/ha. Formulation types WP. PRODUCTS: Discontinued products ‘Lironion’* (Ciba-Geigy). ANALYSIS: Product analysis by acidimetric titration. Residues determined by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >7750 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats >2150 mg/kg. Non-irritating to skin and eyes (rabbits). Inhalation LC 50 (6 h) for rats >0.66 mg/l air. NOEL (90 d) for rats 50 mg/kg daily, for dogs 200 mg/kg daily. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Fish LC 50 (48 h) for trout 5–10 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 c. 12 d. dihydroazadirachtin Insecticide See also The Manual of Biocontrol Agents entry: 2:171 NOMENCLATURE: Chemical Abstracts name 22,23-dihydroazadirachtin; dimethyl [2aR-[2aα,3β,4β(1aR*,2 S*,3aR???*,6aS*,7S*,7aS*),4aβ, 5α,7aS*,8β(E),10β,10aα,10bβ]]-10-(acetyloxy)-4-(hexahydro- 6a-hydroxy-7a-methyl-2,7-methanofuro[2,3-b]oxireno[e]oxepin-1a(2H)-yl)octahydro-3,5- dihydroxy-4-methyl-8-[(2-methyl-1-oxo-2-butenyl)oxy]-1H,7H-naphtho[1,8-bc:4,4a-c′] difuran-5,10a(8H)-dicarboxylate CAS RN [108189–58–8]; [37324–45–1] (unspecifed stereochemistry) O OH CO 2 CH 3 O O CH 3 OC O O OH C CH 3 CH 3 O CH 3 O O O HO CH 3 H O CH 3 C 194 The Pesticide Manual Sixteenth Edition © BCPC 2012 2,3-dihydro-5,6-diphenyl-1,4-oxathi-ine PHYSICAL CHEMISTRY: Mol. wt. 722.7 M.f. C 35 H 46 O 16 APPLICATIONS: Biochemistry Ecdysone antagonist. Uses For control of ants, aphids, Beetles, caterpillars, crickets, etc, on horticultural and ornamental plants. Formulation types WG . MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5 g/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2 g/kg. Non-irritating to skin and eyes (rabbits); not a skin sensitiser (guinea pigs). Inhalation LC 50 for rats >2.9 mg/l. Other Non-mutagenic in reverse mutation, unscheduled DNA synthesis and CHO tests. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail >816 mg/kg. Dietary LD 50 for bobwhite quail >1875 mg/kg. Fish LD 50 (96 h) for rainbow trout 17.65, bluegill sunfsh 9 mg/kg. Daphnia LD 50 11.6 mg/l Bees Relatively non-toxic to honeybees. 2,3-dihydro-5,6-diphenyl-1,4-oxathi-ine Plant growth regulator NOMENCLATURE: IUPAC name 2,3-dihydro-5,6-diphenyl-1,4-oxathi-ine Chemical Abstracts name 2,3-dihydro-5,6-diphenyl-1,4-oxathiin CAS RN [58041–19–3] Development codes P 293 Smiles code C1CS/C(=C(\O1)/ c2ccccc2)/c3ccccc3;without stereochemistry:C1CSC(=C(O1)c2ccccc2)c3ccccc3 PHYSICAL CHEMISTRY: Mol. wt. 254.4 M.f. C 16 H 14 OS COMMERCIALISATION: History Plant growth regulator evaluated by Uniroyal Chemical Co., Inc. 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide Fungicide NOMENCLATURE: IUPAC name 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide Chemical Abstracts name 2,3-dihydro-5-phenyl-1,4-dithiin 1,1,4,4-tetraoxide CAS RN [34407–87–9] Development codes P 368 Smiles code O=S/1(=O)CCS(=O)(=O)/C(=C1)/c2ccccc2;without stereochemistry:O=S1(=O)CCS(=O)(=O)C(=C1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 258.3 M.f. C 10 H 10 O 4 S 2 COMMERCIALISATION: History Fungicide evaluated by Uniroyal Chemical Co., Inc. Supplementary Entries – Extended dimefox 195 dimefox Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name dimefox (BSI, E-ISO, (m) F-ISO) IUPAC name tetramethylphosphorodiamidic fuoride (I) Chemical Abstracts name (I) Other names DMF CAS RN [115–26–4] EC no 204–076–8 Smiles code CN(C)P(=O)(F)N(C)C PHYSICAL CHEMISTRY: Composition Tech. contains schradan (q.v.) and tris(dimethylamino)phosphine oxide. Mol. wt. 154.1 M.f. C 4 H 12 FN 2 OP Form Colourless liquid. B.p. 67 °C /4 mmHg V.p. 48000 mPa (25 °C) K ow logP = 1.2 (chloroform/water) S.g./density 1.115 (20 °C) Solubility Miscible with water and most organic solvents. Stability Resistant to hydrolysis by alkali but is hydrolysed by acids. Slowly oxidised by vigorous oxidising agents, rapidly by chlorine. COMMERCIALISATION: History Insecticide and acaricide reported by H. Kükenthal & G. Schrader (B.I.O.S. Final Report, 1946, 1095). Introduced by Fisons Pest Control Ltd (later Schering Agrochemicals). Patents GB 688760, GB 741662. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide. Uses As a soil treatment for hop plants against aphids and red spider mites. Effective for 42–56 d. PRODUCTS: Discontinued products ‘PestoxXIV’* (Fisons); ‘TerraSytol’* (DuPont); Discontinued mixtures ‘Sytam’* (+ schradan) (with tris(dimethylamino)phosphine oxide) (Murphy, Wacker); ‘Terra Sytam’* (+ schradan) (with tris(dimethylamino)phosphine oxide) (Murphy, Wacker). ANALYSIS: Product analysis, see CIPAC Handbook, 1980, 1A, 329; mixture with schradan, ibid., 334. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1–2 mg/kg. Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R27/28 196 The Pesticide Manual Sixteenth Edition © BCPC 2012 dimethipin dimethipin Herbicide, plant growth regulator NOMENCLATURE: Common name no name (Japan); dimethipin (BSI, ANSI, E-ISO); dimé(thipin) ((m) F-ISO) IUPAC name 2,3-dihydro-5,6-dimethyl-1,4-dithi-ine 1,1,4,4-tetraoxide Chemical Abstracts name 2,3-dihydro-5,6-dimethyl-1,4-dithiin 1,1,4,4-tetraoxide CAS RN [55290–64–7] Development codes N 252 Smiles code CC1=C(C)S(=O)(=O)CCS1(=O)=O PHYSICAL CHEMISTRY: Mol. wt. 210.3 M.f. C 6 H 10 O 4 S 2 Form Tech. is a white, crystalline solid. M.p. 167–169 °C V.p. 0.051 mPa (25 °C) K ow logP = –0.17 (24 °C) Henry 2.33 × 10 –6 Pa m 3 mol –1 (calc.) S.g./density 1.59 g/cm3 (23 °C) Solubility In water 4.6 g/l (25 °C). In acetonitrile 180, methanol 10.7, toluene 8.979 (all in g/l, 25 °C). Stability Stable at pH 3, 6 and 9 (25 °C). Stable for 1 y at 20 °C, 14 d at 55 °C. Stable to light ≥7 d at 25 °C. pKa 10.88, v. weak acid COMMERCIALISATION: History Plant growth regulator reported by R. B. Ames et al. (Proc. Beltwide Cotton Produc. Res. Conf., 1974, p. 61). Introduced by Uniroyal Chemical Co., Inc. (became Chemtura Corp.) in USA in 1982. Patents US 3920438 Manufacturers Chemtura APPLICATIONS: Biochemistry Interferes with protein synthesis in the plant epidermis. Mode of action Defoliant and desiccant. Uses Defoliation of cotton, nursery stock, rubber trees, and vines, at 260–720 g/ha. Potato haulm desiccant, at 480–720 g/ha. Reduces seed moisture content at harvest of maize, rice, oilseed rape, fax, and sunfowers, at 240–720 g/ha. Formulation types SC. PRODUCTS: Discontinued products ‘Harvade’* (Chemtura); ‘Lintplus’* (Chemtura); Discontinued mixtures ‘Leafess’* (+ thidiazuron) (Chemtura). ANALYSIS: Product analysis by glc or i.r. spectrometry. Residues determined by gc/S-FPD (Resid. Anal. Methods). See also Pestic. Anal. Man., II, 180.406, 186.2050. Details available from Chemtura. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Mtg. 101 (2004); JMPR Evaln. I 93 (2001); JMPR Evaln. II 88 (1999), 104 (2004). EU Status (1107/2009) Not approved, 2007/553/EC. S S CH 3 CH 3 O O O O Supplementary Entries – Extended dimethirimol 197 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 500 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >5000 mg/kg. Extreme eye irritant; not a dermal irritant (rabbits). Weak sensitiser (guinea pigs). Inhalation LC 50 (4 h) for rats 1.2 mg/l. NOEL In chronic feeding studies, NOEL for rats 2, dogs 25 mg/kg b.w. daily. ADI/RfD (JMPR) 0.02 mg/kg b.w. [1999, 2004]; (EPA) cRfD 0.02 mg/kg b.w. [1990, 2005]. Toxicity Class WHO (a.i.) III EPA (formulation) I (tech.), III (‘Harvade 5F’ and ‘Harvade 25F’) ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks and bobwhite quail >5000 ppm. LC 50 for mallard ducks 896 mg/kg. Fish LC 50 (96 h) for rainbow trout 52.8, bluegill sunfsh 20.9, sheepshead minnows 17.8 mg/l. Daphnia LC 50 (48 h) 21.3 mg/l. Algae EC 50 (5 d) for Selenastrum capricornutum 5.12 mg/l. Other aquatic spp. LC 50 (96 h) for mysid shrimps (Mysidopsis bahia) 13.9 mg/l. Bees LD 50 >100 μg/bee (25% formulation). Worms LC 50 (14 d) for earthworms >39.4 ppm (25% formulation). ENVIRONMENTAL FATE: Plants Unchanged. Soil/Environment DT 50 in soilc. 104–149 d. Kd 0.092; K oc 3.27. dimethirimol Fungicide FRAC 8, A2 NOMENCLATURE: Common name dimethirimol (BSI, E-ISO, JMAF); dimé(thyrimol) ((m) F-ISO) IUPAC name 5-butyl-2-dimethylamino-6-methylpyrimidin-4-ol Chemical Abstracts name 5-butyl-2-(dimethylamino)-6-methyl-4(1H)-pyrimidinone CAS RN [5221–53–4] Development codes PP675 (ICI) Smiles code CCCCc1c(C)nc(nc1O)N(C)C PHYSICAL CHEMISTRY: Mol. wt. 209.3 M.f. C 11 H 19 N 3 O Form Colourless needles. M.p. 102 °C V.p. 1.46 mPa (30 °C) K ow logP = 1.9 Henry <2.55 × 10 –4 Pa m 3 mol –1 (25 °C, calc.) Solubility In water 1.2 g/l (25 °C). Readily soluble in aqueous solutions of strong acids. In chloroform 1200, xylene 360, ethanol 65, acetone 45 (all in g/l, 25 °C). Stability Stable in acidic and alkaline solutions. Decomposed by sunlight when in aqueous solution; DT 50 c. 7 d. Dissolves in aqueous solutions of strong acids to form water-soluble salts. N N OH CH 3 (CH 2 ) 3 CH 3 N(CH 3 ) 2 198 The Pesticide Manual Sixteenth Edition © BCPC 2012 dimethrin COMMERCIALISATION: History Systemic fungicide reported by R. S. Elias et al. (Nature (London), 1968, 219, 1160). Introduced by ICI Plant Protection Division (later Syngenta AG) and frst marketed in 1970. Patents GB 1182584 Manufacturers Syngenta APPLICATIONS: Biochemistry Inhibits nucleic acid synthesis (adenosine deaminase). Mode of action Systemic fungicide with protective and curative action. Absorbed by the roots, with translocation in the xylem. Uses Soil application for control of powdery mildews in cucurbits, tobacco, capsicums, tomatoes, and some ornamentals, at 0.5–2 kg/ha; also as a foliar spray at 50–100 g/ha.. Formulation types SL . PRODUCTS: Discontinued products ‘Milcurb’* (Syngenta). ANALYSIS: Product analysis by glc (J. E. Bagness & W. G. Sharples, Analyst (London), 1974, 99, 225). Residues determined by hplc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2350, mice 800–1600, guinea pigs 500 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >400 mg/kg. Non-irritating to skin and eyes (rabbits). NOEL (2 y) for dogs 25 mg/kg, for rats 300 mg/kg diet. Other Acute i.p. LD 50 for rats 200–400 mg/kg. Toxicity Class WHO (a.i.) U EPA (formulation) III EC Classifcation (Xn; R21) ECOTOXICOLOGY: Birds Acute oral LD 50 for hens 4000 mg/kg. Fish LC 50 (24 h) for young brown trout 42 mg/l, (48 h) 33 mg/l, (96 h) 28 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Plants In plants, metabolism involves demethylation of the dimethylamino group. Soil/Environment Soil DT 50 c. 120 d (sandy soil, glasshouse and John Innes composts). dimethrin Insecticide IRAC 3 NOMENCLATURE: Common name dimethrin (BSI, E-ISO, ANSI); dimé(thrine) ((f) F-ISO) IUPAC name 2,4-dimethylbenzyl (1RS)-cis,trans-2,2-dimethyl-3-(2-methylprop-1- enyl)cyclopropanecarboxylate; 2,4-dimethylbenzyl (1RS,3RS;1RS,3SR)-2,2-dimethyl- 3-(2-methylprop-1-enyl)cyclopropanecarboxylate; 2,4-dimethylbenzyl (±)-cis-trans- chrysanthemate Supplementary Entries – Extended 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate 199 Chemical Abstracts name (2,4-dimethylphenyl)methyl 2,2-dimethyl-3-(2-methyl-1- propenyl)cyclopropanecarboxylic acid CAS RN [70–38–2] unstated stereochemistry Smiles code CC(=CC1C(C(=O)OCc2ccc(C)cc2C)C1(C)C)C PHYSICAL CHEMISTRY: Mol. wt. 286.4 M.f. C 19 H 26 O 2 COMMERCIALISATION: History Insecticide synthesised by W. F. Barthel, activity reported by P. G. Piquett & W. A. Gersdorff (J. Econ. Entomol., 1958, 51, 791). APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 4 (1965). MAMMALIAN TOXICOLOGY: NOEL (1 y) for rats 300 mg/kg b.w. (EPA Tracking). ADI/RfD (JMPR) No ADI [1965]; (EPA) 0.3 mg/kg b.w. [1986]. 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate Insecticide NOMENCLATURE: IUPAC name 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (I) Chemical Abstracts name (I) CAS RN [7122–04–5] Development codes C 10 015 Smiles code CNC(=O)Oc1ccccc1C2OC(C)C(C)O 2 PHYSICAL CHEMISTRY: Mol. wt. 251.3 M.f. C 13 H 17 NO 4 COMMERCIALISATION: History Insecticide reported by F. Bachmann & J. B. Legge (J. Sci. Food Agric., 1968 Suppl., p. 39). Introduced by Ciba AG (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact and ingested insecticide. PRODUCTS: Discontinued products ‘Fondaren’* (Ciba-Geigy); ‘Sapecron C’* (Ciba). 200 The Pesticide Manual Sixteenth Edition © BCPC 2012 dimetilan 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate Insecticide NOMENCLATURE: IUPAC name 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate Chemical Abstracts name 5,5-dimethyl-3-oxo-1-cyclohexen-1-yl dimethylcarbamate Other names dimetan CAS RN [122–15–6] EC no 204–525–8 Development codes G 19 258 Smiles code CN(C)C(=O)OC1=CC(=O)CC(C)(C)C1 PHYSICAL CHEMISTRY: Mol. wt. 211.3 M.f. C 11 H 17 NO 3 COMMERCIALISATION: History Insecticide introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Dimetan’* (Geigy). MAMMALIAN TOXICOLOGY: EC Classifcation T; R25 dimetilan Insecticide NOMENCLATURE: Common name dimetilan (BSI, ESA) IUPAC name 1-dimethylcarbamoyl-5-methylpyrazol-3-yl dimethylcarbamate Chemical Abstracts name 1-[(dimethylamino)carbonyl]-5-methyl-1H-pyrazol-3-yl dimethylcarbamate CAS RN [644–64–4] EC no 211–420–0 Development codes G 22 870; GS 13 332 Smiles code CN(C)C(=O)Oc1cc(C)n(n1)C(=O)N(C)C PHYSICAL CHEMISTRY: Composition Tech. is >96%. Mol. wt. 240.3 M.f. C 10 H 16 N 4 O 3 Form Colourless solid; (tech. is a light yellow to reddish-brown crystalline solid). M.p. 68–71 °C; (tech., 55– 65 °C) B.p. 200–210/13 mmHg V.p. 13 mPa (20 °C) Solubility Readily soluble in water, chloroform, DMF; soluble in ethanol, acetone, xylene and other organic solvents. Stability Hydrolysed by acids and by alkalis. COMMERCIALISATION: History Insecticide reported by H. Gysin (Chimia, 1954, 8, 205, 221). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). Patents CH 281946, CH 282655, GB 681376, US 2681879. Supplementary Entries – Extended dimexano 201 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Ingested insecticide. Uses For control of fies. PRODUCTS: Discontinued products ‘Snip’* (Ciba-Geigy). ANALYSIS: Product analysis is by glc with internal standard. Residues may be determined by glc with MCD or by tlc. See also A. Margo & K. Stammbach, Anal. Methods Pestic. Plant Growth Regul. Food Addit., 1964, 2, 183; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 376. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 64, mice 60–65 mg/kg. Livestock is more susceptible. Toxicity Class WHO (a.i.) Ib EC Classifcation T; R25| Xn; R21| N; R50, R53 dimexano Herbicide, plant growth regulator NOMENCLATURE: Common name dimexano (BSI (from 1984), E-ISO, (m) F-ISO); dimexan* (BSI before 1984) IUPAC name O,O-dimethyl dithiobis(thioformate) Chemical Abstracts name dimethyl thioperoxydicarbonate Other names dimethylxanthic disulfde CAS RN [1468–37–7] EC no 215–993–8 Smiles code COC(=S)SSC(=S)OC PHYSICAL CHEMISTRY: Composition Tech. isc. 96%. Mol. wt. 214.3 M.f. C 4 H 6 O 2 S 4 Form Tech. is a yellow oil, with an objectionable odour. V.p. 4 × 10 5 mPa (21 °C) S.g./density 1.394 (20 °C, tech.) Solubility Miscible with acetone, benzene, ethanol, hexane. COMMERCIALISATION: History Herbicide introduced by Vondelingenplaat N.V. APPLICATIONS: Mode of action Contact herbicide, plant growth regulator and desiccant. Uses At 9 kg/ ha pre-em. on drilled crops, controlling seeding dicotolydonous weeds; at ≤28 gk/ha as a pre-harvest desiccant of onions and peas; and to control the growth and splitting of carrots. Formulation types EC. 202 The Pesticide Manual Sixteenth Edition © BCPC 2012 dinex; dinex-diclexine PRODUCTS: Discontinued products ‘TriPE’* (Vondelingenplaat). ANALYSIS: Product analysis is by colorimetry (D. G. Clarke et al., Anal. Chem., 1951, 23, 1842) after reduction. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 340 mg tech./kg. Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22| N; R50, R53 ENVIRONMENTAL FATE: Soil/Environment It does not persist in soil. dimidazon Herbicide NOMENCLATURE: Common name dimidazon (BSI, E-ISO); dimethazone* (withdrawn BSI name); dimidazone ((m) F-ISO) IUPAC name 4,5-dimethoxy-2-phenylpyridazin-3(2H)-one Chemical Abstracts name 4,5-dimethoxy-2-phenyl-3(2H)-pyridazinone CAS RN [3295–78–1] Development codes BAS 255H (BASF) Smiles code COc1cnn(c2ccccc2)c(=O)c1OC PHYSICAL CHEMISTRY: Mol. wt. 232.2 M.f. C 12 H 12 N 2 O 3 COMMERCIALISATION: History Herbicide introduced by BASF AG. dinex; dinex-diclexine Acaricide, insecticide NOMENCLATURE: Common name dinex (BSI, E-ISO, (m) F-ISO); DN (JMAF); pé(dinex) ((m) France) IUPAC name 2-cyclohexyl-4,6-dinitrophenol (I) Chemical Abstracts name (I) Other names DNOCHP (dinex) CAS RN [131–89–5] dinex; [317–83–9] dinex-diclexine EC no 205–042–5 Development codes DN1 (dinex); DN111 (dinex-diclexine) PHYSICAL CHEMISTRY: Mol. wt. 266.3; (dinex-diclexine 447.6) M.f. C 12 H 14 N 2 O 5 ; (dinex-diclexine C24H37N3O5) Supplementary Entries – Extended dinofenate 203 COMMERCIALISATION: History Dinex was introduced as an acaricide and insecticide by Dow Chemical Co., Ltd (later DowElanco), and its dicyclohexylammonium salt (dinex-diclexine) by Fisons Ltd (later Schering Agriculture). PRODUCTS: Discontinued products ‘DynoneII’* (FBC). MAMMALIAN TOXICOLOGY: ADI/RfD (EPA) 0.002 mg/kg b.w. [1987], based on other dinitrophenols. Toxicity Class WHO (a.i.) O EC Classifcation T; R23/24/25| N; R50, R53 (dinex and dinex salts and esters) dinocton Acaricide, fungicide NOMENCLATURE: Common name dinocton (BSI, E-ISO, (m) F-ISO, for a reaction product comprising isomeric dinitro(octyl)phenyl methyl carbonates) IUPAC name for main components: (i) 2,4-dinitro-6-(1-propylpentyl)phenyl methyl carbonate (I); (ii) 2-(1-ethylhexyl)-4,6-dinitrophenyl methyl carbonate (II); (iii) 2,6-dinitro-4- (1-propylpentyl)phenyl methyl carbonate (III); (iv) 4-(1-ethylhexyl)-2,6-dinitrophenyl methyl carbonate (IV) Chemical Abstracts name (I), (II), (III), (IV) Other names dinocton-6 (i) + (ii); dinocton-4 (iii) + (iv) CAS RN [32534–96–6] (i) + (ii); [19000–58–9] (i); [19000–52–3] (ii); [32535–08–3] (iii) + (iv); [6465–51–6] (iii); [6465–60–7] (iv) Development codes MC 1945 (i) + (ii); MC 1947 (iii) + (iv); TD 8537 (iii) + (iv) PHYSICAL CHEMISTRY: Mol. wt. 354.4 M.f. C 16 H 22 N 2 O 7 COMMERCIALISATION: History Acaricide and fungicide reported by M. Pianka (Proc. Crop Prot. Symp., 2nd., Magdeburg, 1966). Evaluated by Murphy Chemical Co. (later DowElanco). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22| N; R50, R53 dinofenate Herbicide NOMENCLATURE: Common name dinofenate (BSI) IUPAC name 2-sec-butyl-4,6-dinitrophenyl 2,4-dinitrophenyl carbonate 204 The Pesticide Manual Sixteenth Edition © BCPC 2012 dinoprop Chemical Abstracts name 2,4-dinitrophenyl 2-(1-methylpropyl)-4,6-dinitrophenyl carbonate CAS RN [61614–62–8] Smiles code CCC(C)c1cc(cc([N+](=O)[O-]) c1OC(=O)Oc2ccc(cc2[N+](=O)[O-])[N+](=O)[O-])[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 450.3 M.f. C 17 H 14 N 4 O 11 COMMERCIALISATION: History Herbicide evaluated by Pennwalt. dinopenton Acaricide, fungicide NOMENCLATURE: Common name dinopenton (BSI, E-ISO, (m) F-ISO) IUPAC name isopropyl 2-(1-methylbutyl)-4,6-dinitrophenyl carbonate Chemical Abstracts name 2-(1-methylbutyl)-4,6-dinitrophenyl 1-methylethyl carbonate CAS RN [5386–57–2] Smiles code CCCC(C)c1cc(cc([N+](=O)[O-])c1OC(=O)OC(C)C)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 340.3 M.f. C 15 H 20 N 2 O 7 COMMERCIALISATION: History Acaricide reported at 5th Int. Pestic. Congr., London, 1963 (M. Pianka, J. Sci. Food Agric., 1966, 17, 47). Evaluated by Murphy Chemical Ltd (later DowElanco). dinoprop Herbicide NOMENCLATURE: Common name dinoprop (BSI, E-ISO, (m) F-ISO) IUPAC name 4,6-dinitro-o-cymen-3-ol Chemical Abstracts name 3-methyl-2-(1-methylethyl)-4,6-dinitrophenol Other names DNOIPP CAS RN [7257–41–2] Smiles code CC(C)c1c(C)c(cc([N+] (=O)[O-])c1O)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 240.2 M.f. C 10 H 12 N 2 O 5 COMMERCIALISATION: History Herbicide and insecticide. Supplementary Entries – Extended dinoseb 205 dinosam Herbicide NOMENCLATURE: Common name dinosame ((m) F-ISO); dinosam (BSI, E-ISO) IUPAC name 2-(1-methylbutyl)-4,6-dinitrophenol (I) Chemical Abstracts name (I) Other names DNAP; DINOSAP CAS RN [4097–36– 3] Smiles code CCCC(C)c1cc(cc([N+](=O)[O-])c1O)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 254.2 M.f. C 11 H 14 N 2 O 5 COMMERCIALISATION: History Herbicide reported by A. S. Crafts (Plant Physiol., 1946, 21, 345). Introduced by Standard Agricultural Chemicals Inc. PRODUCTS: Discontinued products ‘Sinox General’* (Standard). MAMMALIAN TOXICOLOGY: EC Classifcation T; R23/24/25| N; R50, R53 (dinosam or its salts and esters) dinoseb Herbicide, insecticide HRAC M WSSA 24; dinitrophenol NOMENCLATURE: Common name dinoseb (BSI, E-ISO, ANSI, WSSA); dinosè(be) ((m) F-ISO); DNBP (JMAF) IUPAC name 2-sec-butyl-4,6-dinitrophenol Chemical Abstracts name 2-(1-methylpropyl)-4,6-dinitrophenol CAS RN [88– 85–7] EC no 201–861–7 Development codes DN 289 (Dow); Hoe 26 150 Smiles code CCC(C)c1cc(cc([N+](=O)[O-])c1O)[N+](=O)[O-] PHYSICAL CHEMISTRY: Composition Tech. is 95–98%. Mol. wt. 240.2 M.f. C 10 H 12 N 2 O 5 Form Orange solid; (tech., orange-brown solid). M.p. 38–42 °C; (tech.: 30–40 °C) V.p. 0.13 mPa (room temperature) (Adv. Chem. Series, ACS, cited in ARS PPD) K ow logP = 2.29 (unstated pH) (Agchem. Desk Ref.) Henry 6.0 × 10 –4 Pa m 3 mol –1 (20 °C, calc.) S.g./density 1.265 (45 °C) Solubility In water 52 mg/l (20 °C). Soluble in most organic solvents and in petroleum oils. In ethanol 480, heptane 270 (both in g/kg). pKa 4.62 F.p. 177 °C O 2 N NO 2 OH CHCH 2 CH 3 CH 3 206 The Pesticide Manual Sixteenth Edition © BCPC 2012 dinoseb COMMERCIALISATION: History Herbicidal activity reported by A. S. Crafts (Science, 1945, 101, 417). Introduced by Dow Chemical Co. (later DowElanco). Patents US 2192197 (to Dow); DE 1088757; GB 909732 (both to Hoechst) APPLICATIONS: Biochemistry Inhibits respiratory electron transport, and uncouples oxidative phosphorylation. Mode of action Selective non-systemic herbicide with contact action. Uses Dinoseb was used as the ammonium or an amine salt or acetate ester for post- emergence weed control in cereals, undersown cereals, seedling alfalfa and peas at ≤2.5 kg/ha. Solutions of dinoseb in oil were used for pre-emergence control of annual weeds in beans, peas and potatoes, for pre-harvest desiccation of hops, leguminous seed crops and potatoes and for control of runners and suckers in raspberries and strawberries. Dinoseb acetate was also used in combination with monolinuron pre-emergence in dwarf beans and potatoes. Phytotoxicity Phytotoxic to cruciferous crops. Formulation types SL; EC; EO. PRODUCTS: Discontinued products ‘Aretit’* (Hoechst); ‘Fanicide’* (La Littorale); ‘Farmon Desicoil 25’* (Farm Protection); ‘General Weedkiller’* (Vertac); ‘Ivosit’* (Hoechst); ‘Persevtox’* (La Quinoléine); ‘Premerge’* (olamine and 2-hydroxypropylammonium salts) (Siapa, Tifa, Vertac); ‘Premerge 3’* (olamine and diolamine salts) (Siapa, Tifa, Vertac); ‘Selective Weedkiller’* (ammonium salt) (Vertac); ‘Supersevtox’* (diolamine and trolamine salts) (Schering). ANALYSIS: Product analysis by titration of a deriviative (CIPAC Handbook, 1994, F, 327) or by colorimetry of solutions in alkali (D. S. Farrington et al., Analyst (London), 1983, 108, 353). Residues determined by glc of a derivative (Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 639). See also Pestic. Anal. Man., I, 208. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.149 (1994). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEC as amended by 90/533/EEC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 58, guinea pigs 25 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 80–200, guinea pigs 500 mg/kg. Mild skin and eye irritant (rabbits). NOEL In 6 mo feeding trials, rats receiving 100 mg/kg diet showed no ill-effects. ADI/RfD (EPA) cRfD 0.001 mg/kg b.w. [1989]. Water GV Excluded from GV derivation (U). Other Very toxic to man (uncouples oxidative phosphorylation). Toxicity Class WHO (a.i.) Ib EC Classifcation R44| T; R24/25| R61| R62| Xi; R36| N; R50, R53 PIC Yes. ECOTOXICOLOGY: Birds Acute oral LD 50 for chickens 26 mg/kg. Dietary LC 50 (5 d) for Japanese quail 409, ring-necked pheasant 515 mg/kg diet. Fish Highly toxic to fsh. Bees Toxic to bees. Supplementary Entries – Extended dinoseb acetate 207 ENVIRONMENTAL FATE: Animals In mammals, undergoes oxidation of the sec-butyl side-chain, conjugation, and in rats (but not in mice) reduction of either of the nitro groups and acetylation of the amino group formed. Soil/Environment Under normal conditions of use, persistence in soil isc. 2–6 weeks. dinoseb acetate Herbicide NOMENCLATURE: Common name dinoseb acetate (BSI, ISO-E, ANSI, WSSA); dinosè(b acé) ((m) F-ISO); DNBPA (JMAF) IUPAC name 2-sec-butyl-4,6-dinitrophenyl acetate Chemical Abstracts name 2-(1-methylpropyl)-4,6-dinitrophenyl acetate CAS RN [2813–95–8] Development codes Hoe 02904 Smiles code CCC(C)c1cc(cc([N+](=O)[O-])c1OC(=O)C)[N+](=O)[O-] PHYSICAL CHEMISTRY: Composition Tech. isc. 94%. Mol. wt. 282.2 M.f. C 12 H 14 N 2 O 6 Form Brown oil with an aromatic vinegar-like odour; (tech. is a viscous brown oil). M.p. 26–27 °C B.p. 170 °C /4 mmHg V.p. 28 mPa (43 °C); 183 mPa (60 °C) Solubility In water 2.2 g/l (20 °C). Readily soluble in aromatic solvents. Stability Hydrolysed by acids and alkalis, and slowly hydrolysed in neutral media. COMMERCIALISATION: History Herbicidal activity reported by H. Härtel (Meded. Landbouwhogesch. Opzoekingsstn. Staat Gent, 1960, 25, 1422). Introduced by Hoechst AG (later AgrEvo GmbH). APPLICATIONS: Biochemistry Inhibits respiratory electron transport, and uncouples oxidative phosphorylation. Mode of action Selective non-systemic herbicide with contact action. Uses See dinoseb. Formulation types EC; WP. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Ivocit’* (Hoechst); ‘Phenotan’* (Rhône-Poulenc). ANALYSIS: Product by spectrophotometry (D. S. Farrington et al., Analyst (London) 1983, 108 1284, 353–360; CIPAC Handbook, 1970, 1, 337–341). By coulometry (B. G. Kratochvil & I. M. Al- Daher Analyst (London) 1981, 106(1264), 796–799). Residues by GLC of a derivative with ECD (Anal. Methods Pestic. Plant Growth Regul. 1972, 6, 639), or by spectrophotometry (ibid. 1967, 5, 390). 208 The Pesticide Manual Sixteenth Edition © BCPC 2012 dinoterb TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.882 (1997). EU Status (1107/2009) See dinoseb. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 60–65 mg/kg. Inhalation LC 50 (4 h) for rats 1.3 mg/l air. NOEL (2 y) for rats 100 mg/kg diet, for dogs 8 mg/kg diet. Other Very toxic to man (uncouples oxidative phosphorylation). Toxicity Class WHO (a.i.) Ib EC Classifcation R44| R61| R62| T; R24/25| Xi; R36| N; R50, R53 PIC Yes. ECOTOXICOLOGY: Fish Toxic to fsh. Bees Toxic to bees. ENVIRONMENTAL FATE: Animals Rapidly degraded to dinoseb (q.v.). dinosulfon Acaricide, fungicide NOMENCLATURE: Common name dinosulfon (BSI, E-ISO, (m) F-ISO) IUPAC name S-methyl O-2-(1-methylheptyl)-4,6-dinitrophenyl thiocarbonate Chemical Abstracts name S-methyl O-[2-(1-methylheptyl)-4,6- dinitrophenyl] carbonothioate CAS RN [5386–77–6] unstated stereochemistry Development codes MC 1143 Smiles code CCCCCCC(C)c1cc(cc([N+](=O)[O-])c1OC(=O)SC)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 370.4 M.f. C 16 H 22 N 2 O 6 S COMMERCIALISATION: History Acaricide and fungicide reported by M. Pianka & J. D. Edwards (J. Sci. Food Agric., 1968, 19, 60) and M. Pianka & P. J. J. Sweet (ibid., pp. 672, 676). Evaluated by Murphy Chemical Co. (later DowElanco). dinoterb Herbicide HRAC M WSSA 24; dinitrophenol NOMENCLATURE: Common name dinoterbe ((m) F-ISO); dinoterb (BSI, E-ISO) OH C(CH 3 ) 3 O 2 N NO 2 Supplementary Entries – Extended dinoterb 209 IUPAC name 2-tert-butyl-4,6-dinitrophenol Chemical Abstracts name 2-(1,1-dimethylethyl)-4,6-dinitrophenol Other names DNTBP CAS RN [1420–07–1] EC no 215–813–8 Development codes LS63 133 (Rhône-Poulenc) Smiles code CC(C)(C)c1cc(cc([N+] (=O)[O-])c1O)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 240.2 M.f. C 10 H 12 N 2 O 5 Form Pale yellow solid, with a phenol-like odour. M.p. 125.5–126.5 °C V.p. 20 mPa (20 °C) Henry 1.07 Pa m 3 mol –1 (calc.) Solubility In water 4.5 mg/l (pH 5, 20 °C). In cyclohexanone, ethyl acetate, DMSOc. 200 g/kg. In alcohols, glycols, aliphatic hydrocarbonsc. 100 g/kg. Soluble in aqueous alkalis with the formation of salts. Stability Stable below the melting point. Decomposes above 220 °C. Stable at least 34 d at pH 5–9 (22 °C). COMMERCIALISATION: History Herbicide reported by G. A. Emery et al. (Proc. Conf. EWRC/COLUMA, 2nd, 1965, p. 41) (for acetate) and by P. Poignant & P. Crisinel (C. R. Journ. Etud. Herbic. Conf. COLUMA, 4th, 1967, p. 196). Introduced by Pépro (now Bayer AG) and by Murphy Chemical Ltd (who no longer manufacture or market it). Patents FR 1475686; FR 1532332; GB 1126658; US 3565601 (all to Pépro) Manufacturers Bayer CropScience APPLICATIONS: Biochemistry Oxidative phosphorylation uncoupler, leading to membrane disruption. Mode of action Selective non-systemic herbicide with contact action. Uses Control of annual broad-leaved weeds post-emergence in cereals, maize, alfalfa, and beet; and pre- emergence in peas and beans. Also used for destruction of potato haulms. Formulation types EC; SL . ANALYSIS: Product analysis by methylation with diazomethane followed by glc (CIPAC Handbook, 1983, 1B, 1797). Residues by glc; details available from Bayer CropScience. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Rev. Rep. 8083/VI/97 (1997). EU Status (1107/2009) Not approved, 98/269/EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 62, mice 25, rabbits 28 mg/kg. Skin and eye Acute percutaneous LD 50 for guinea pigs 150 mg/kg. NOEL (2 y) for rats 0.375 mg/kg diet. ADI/RfD (ECCO) No ADI [1997]. Toxicity Class WHO (a.i.) Ib. EC Classifcation R61| T+; R28| T; R24| R44| N; R50, R53: (salts and esters are R61| T+; R28| T; R24| N; R50, R53) ECOTOXICOLOGY: Fish LC 50 (96 h) for rainbow trout 0.0034 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Animals In rats, following oral administration, 98% is excreted in the faeces and urine within 7 days. 210 The Pesticide Manual Sixteenth Edition © BCPC 2012 diofenolan dinoterbon Acaricide, fungicide NOMENCLATURE: Common name dinoterbon (BSI, E-ISO, (m) F-ISO) IUPAC name 2-tert-butyl-4,6-dinitrophenyl ethyl carbonate Chemical Abstracts name 2-(1,1-dimethylethyl)-4,6-dinitrophenyl ethyl carbonate CAS RN [6073–72–9] Smiles code CCOC(=O)Oc1c(cc(cc1C(C)(C)C)[N+](=O)[O-])[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 312.3 M.f. C 13 H 16 N 2 O 7 COMMERCIALISATION: History Acaricide and fungicide reported at 5th Int. Pestic. Congr., London, 1963 (M. Pianka, J. Sci. Food Agric., 1966, 17, 47). Evaluated by Murphy Chemical Co. (later DowElanco). diofenolan Insecticide NOMENCLATURE: Common name diofé(nolane) ((m) F-ISO); diofenolan (BSI, E-ISO) IUPAC name A mixture of: (2RS,4SR)-4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether (50–80%) and (2RS,4RS)-4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether (50–20%) Chemical Abstracts name A mixture of (2RS,4SR)-2-ethyl-4-[(4-phenoxyphenoxy) methyl]-1,3-dioxolane and (2RS,4RS)-2-ethyl-4-[(4-phenoxyphenoxy)methyl]- 1,3-dioxolane CAS RN [63837–33–2] Development codes CGA 059 205 Smiles code CCC1OCC(COc2ccc(Oc3ccccc3)cc2)O1 PHYSICAL CHEMISTRY: Composition A mixture of 50–80% (2RS,4SR)- isomer with 50–20% (2RS,4RS)- isomer. Mol. wt. 300.3 M.f. C 18 H 20 O 4 Form Clear, pale yellow viscous liquid. B.p. >250 °C /101.325 kPa (OECD 103) V.p. 1.1 × 10 –1 mPa (25 °C) (OECD 104) K ow logP = 4.8; 4.4 (cis- isomer); 4.3 (trans- isomer) (25 °C) (OECD 117) Henry 6.74 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.141 (20 °C) Solubility In water 4.9 mg/l (25 °C) (OECD 105). Miscible with methanol, acetone, toluene, hexane, n-octanol. Stability Hydrolytically stable at pH ≥7. Rapidly degraded by light. pKa No dissociation in range pH 1–11 O O O CH 2 CH 3 O CH 2 Supplementary Entries – Extended dioxabenzofos 211 COMMERCIALISATION: History Reported by H. P. Streibert et al. (Proc. Br. Crop Prot. Conf. - Pests Dis., 1994, 1, 23). Introduced by Ciba-Geigy AG (later Novartis Crop Protection AG). Manufacturers Novartis APPLICATIONS: Mode of action Insect growth regulator with juvenile hormone activity. Inhibits development of frst and second instar larvae of scales. Uses Active against most scale insects and eggs of some Lepidoptera in citrus, pome fruit, stone fruit, grapes, mango, olives, nuts, tea and ornamentals. Formulation types EC. PRODUCTS: Discontinued products ‘Arbor’* (Novartis); ‘Aware’* (Ciba); ‘Context’* (Ciba). ANALYSIS: By hplc with uv detection. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats (24 h) >2000 mg/kg. Not irritant to skin or eyes (rabbits). Not a skin sensitiser. Inhalation LC 50 (4 h) for rats >3100 mg/m 3 . NOEL (3 mo) for rats 12 mg/kg b.w.; NOAEL (3 mo) for dogs 12 mg/kg b.w.. ADI/RfD 0.006 mg/kg (provisional). Toxicity Class WHO (a.i.) III ECOTOXICOLOGY: Birds Acute oral LC 50 for quail and ducks >2000 mg/kg. Fish LC 50 (96 h) for bluegill sunfsh, catfsh, carp and trout 1.0–1.7 mg/l. Daphnia LC 50 (48 h) 0.5 mg/l. Algae LC 50 (72 h) 0.072 mg/l. Bees LD 50 (48 h, oral and contact) >96 mg/bee. Tech. material has a high toxicity to the brood of the honeybee. Worms LC 50 (14 d) 204 mg/kg soil. ENVIRONMENTAL FATE: Animals Intestinal absorption 80%. Rapid elimination. Tissue residues low. Soil/Environment Rapid dissipation: feld trials DT 50 c. 6 d; laboratory DT 50 <2 d. No potential for mobility (RMF 0.15). dioxabenzofos Insecticide IRAC 1B NOMENCLATURE: Common name dioxabenzofos (BSI, E-ISO, (m) F-ISO); salithion (JMAF) O P O OCH 3 S 212 The Pesticide Manual Sixteenth Edition © BCPC 2012 dioxabenzofos IUPAC name (RS)-2-methoxy-4H-1,3,2λ5-benzodioxaphosphinine 2-sulfde; (RS)-2- methoxy-4H-1,3,2λ5-benzodioxaphosphorine 2-sulfde Chemical Abstracts name (±)-2-methoxy-4H-1,3,2-benzodioxaphosphorin 2-sulfde CAS RN [3811–49–2] unstated stereochemistry EC no 223–292–3 Smiles code COP1(=S)OCc2ccccc2O1 PHYSICAL CHEMISTRY: Mol. wt. 216.2 M.f. C 8 H 9 O 3 PS Form Tech. is a light yellow powder. M.p. 52.5–54 °C V.p. 420 mPa (20 °C) Henry 2.11 Pa m 3 mol –1 (calc.) Solubility In water 43 mg/l (20 °C). In acetonitrile, cyclohexanone, xylene >1 (all in kg/kg, 21–23 °C). Stability Stable in acidic to weakly alkaline media (pH 2–8). COMMERCIALISATION: History Insecticide reported by M. Eto & Y. Oshima (Agric. Biol. Chem., 1962, 26, 452). Introduced by Sumitomo Chemical Co., Ltd. Patents JP 467645; JP 446747; GB 987378; FR 1360130 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide with contact, ingested and respiratory action. Uses Control of a wide range of boring, chewing and sucking insects (Aphididae, Coccidae, Chilo spp., Curculionidae, Diaspididae, Margarodidae, Lepidoptera, Plutella xylostella and Spodoptera spp.) in fruit, rice, tea, tobacco and vegetables. Formulation types MG; EC; WP; GR; GP. Compatibility Incompatible with strongly alkaline materials. PRODUCTS: Discontinued products ‘Salithion’* (Sumitomo Chemical). ANALYSIS: Product analysis by glc. Residues determined by glc with FPD (M. Eto & J. Miyamoto, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 431). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 125, female rats 180, male mice 125 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats 400, mice >1250 mg/kg. Toxicity Class WHO (a.i.) II EC Classifcation T; R24/25, R39/25| N; R51, R53 ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 7.8 mg/l. Supplementary Entries – Extended dioxacarb 213 dioxacarb Insecticide IRAC 1A NOMENCLATURE: Common name dioxacarb (BSI, E-ISO, ANSI, ESA, JMAF); dioxacarbe ((m) F-ISO) IUPAC name 2-(1,3-dioxolan-2-yl)phenyl methylcarbamate Chemical Abstracts name 2-(1,3-dioxolan-2-yl)phenyl methylcarbamate CAS RN [6988–21–2] EC no 230–253–4 Development codes C 8353 Smiles code CNC(=O)Oc1ccccc1C2OCCO 2 PHYSICAL CHEMISTRY: Mol. wt. 223.2 M.f. C 11 H 13 NO 4 Form Colourless crystals. M.p. 114–115 °C V.p. 0.04 mPa (20 °C) Henry 1.49 × 10 –6 Pa m 3 mol –1 (calc.) S.g./density 1.46 (20 °C) Solubility In water 6 g/l (20 °C). In acetone 280, cyclohexanone 235, DMF 550, dichloromethane 345, ethanol 80, xylene 9, hexane 0.18 (all in g/l, 20 °C). Stability Relatively stable in neutral media, but decomposed in acidic and alkaline media; DT 50 (calc., 20 °C) 85 h (pH 5), 24.6 d (pH 7), 15 h (pH 9). COMMERCIALISATION: History Insecticide reported by F. Bachmann & J. B. Legge (J. Sci. Food Agric., Suppl., 1968, p. 39). Introduced by Ciba AG (later Ciba-Geigy AG). Patents BE 670630; GB 1122633 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Insecticide with contact and stomach action. Gives rapid knockdown. Uses Control of cockroaches (including those resistant to organochlorine and organophosphorus insecticides), fies, Bed bugs, and other public health pests in household use, animal houses, industrial areas, and stored products. Control of chewing and sucking foliar insect pests on a range of crops. Particular uses included control of colorado beetle on potatoes, leafhoppers and planthoppers on rice, capsid bugs on cocoa, and various Beetles on oilseed rape. Formulation types WP; EC. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Dimox’* (Chimitox); ‘Elocron’* (Ciba-Geigy); ‘Famid’* (Ciba- Geigy). ANALYSIS: Product analysis by acidimetric titration (A. Becker & W. Zeizler, Fresenius’ Z. Anal. Chem., 1971, 257, 125). Residues determined by glc with ECD of a derivative. O O O C O CH 3 NH 214 The Pesticide Manual Sixteenth Edition © BCPC 2012 dioxathion TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 72 mg/kg. Skin and eye Acute percutaneous LD 50 for ratsc. 3000, rabbits 1950 mg/kg. Inhalation LC 50 for ratsc. 0.16 mg/l air. NOEL (90 d) for rats 10 mg/kg daily; for dogs 2 mg/kg daily (marginal). Toxicity Class WHO (a.i.) II EPA (formulation) II EC Classifcation T; R25| N; R51, R53 ECOTOXICOLOGY: Birds Slightly toxic to birds. Fish LC 50 (96 h) for rainbow trout 29, carp 32 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, dioxacarb is rapidly absorbed and oxidised to the N-methylol and hydrolysed to the corresponding phenol. Both breakdown products are eliminated as conjugates (e.g. glycosides), 85–90% elimination occurring within 24 h. Plants In plants, persists on foliage for c. 5–7 d. Soil/Environment Dioxacarb is rapidly decomposed in soil. Persists on wall surfaces for up to 6 months. dioxathion Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name dioxane phosphate (JMAF); delnav * (former exceptions: Turkey, USSR); dioxathion (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name S,S′-(1,4-dioxane-2,3-diyl) O,O,O′,O′-tetraethyl bis(phosphorodithioate) Chemical Abstracts name S,S′-1,4-dioxane-2,3-diyl bis(O,O-diethyl phosphorodithioate) CAS RN [78–34–2] EC no 201–107–7 Development codes Hercules AC258 Smiles code CCOP(=S)(OCC)SC1OCCOC1SP(=S)(OCC)OCC PHYSICAL CHEMISTRY: Composition Tech. is 68–75%: 24% cis- , 48% trans- isomers,c. 30% related compounds. Mol. wt. 456.5 M.f. C 12 H 26 O 6 P 2 S 4 Form Tech. is a brown liquid. S.g./density 1.257 (26 °C) Solubility Insoluble in water. In hexane, kerosene 10 g/kg; soluble in most organic solvents. Stability Stable in water at neutral pH, but hydrolysed by alkali or on heating. Unstable to iron or tin surfaces or when mixed with certain carriers. COMMERCIALISATION: History Insecticide reported by W. R. Diveley et al. (J. Am. Chem. Soc., 1959, 81, 139). The cis- is more toxic than the trans- isomer to fies and rats (B. W. Arthur & J. E. Casida, J. Supplementary Entries – Extended diphenyl sulfone 215 Econ. Entomol., 1959, 52, 20). Introduced by Hercules Inc. (later by Nor-Am Chemical Co.). Patents US 2725328; US 2815350 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact insecticide and acaricide. Uses For treatment of livestock to control ectoparasites, including ticks and biting fies. It was also used for residual control of chigoes, feas, mites and ticks in parks and recreation areas. Formulation types EC. PRODUCTS: Discontinued products ‘Delnav’* (NOR-AM); ‘Deltic’* (NOR-AM). ANALYSIS: Product analysis by i.r. spectroscopy. Residues determined by glc (D. C. Abbott et al., Pestic. Sci., 1970, 1, 10). See also Pestic. Anal. Man., II, 186.2450. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Evaln. 11 (1968), 19 (1972). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male albino rats 43, female rats 23 mg/kg. Skin and eye Acute percutaneous LD 50 for male albino rats 235, female albino rats 63 mg/kg. NOEL Cholinesterase inhibition was observed in female rats receiving 10 mg/kg diet. ADI/RfD (JMPR) 0.0015 mg/kg b.w. [1968]. Toxicity Class WHO (a.i.) Ib EC Classifcation T+; R26/28| T; R24| N; R50, R53| concn. dep. diphenyl sulfone Acaricide NOMENCLATURE: Common name diphé(nylsulfone) (F-ISO, accepted in lieu of a common name.); diphenyl sulfone (BSI, E-ISO) IUPAC name diphenyl sulfone Chemical Abstracts name 1,1′-sulfonylbis[benzene] Other names DPS CAS RN [127–63–9] Smiles code O=S(=O)(c1ccccc1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 218.3 M.f. C 12 H 10 O 2 S COMMERCIALISATION: History Acaricide reported by J. K. Eaton & R. G. Davies (Ann. Appl. Biol., 1950, 37, 471). 216 The Pesticide Manual Sixteenth Edition © BCPC 2012 dipropetryn dipropetryn Herbicide NOMENCLATURE: Common name dipropetryn (BSI, E-ISO, ANSI, WSSA); dipropé(tryne) ((f) F-ISO) IUPAC name 6-ethylthio-N 2 ,N4-diisopropyl-1,3,5-triazine-2,4-diamine Chemical Abstracts name 6-(ethylthio)-N,N′-bis(1-methylethyl)-1,3,5- triazine-2,4-diamine CAS RN [4147–51–7] Development codes GS 16 068 Smiles code CCSc1nc(NC(C)C)nc(NC(C)C)n1 PHYSICAL CHEMISTRY: Mol. wt. 255.4 M.f. C 11 H 21 N 5 S Form Colourless powder. M.p. 104–106 °C V.p. 0.097 mPa (20 °C) K ow logP = 3.810 Henry 1.55 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.120 (20 °C) Solubility In water 16 mg/l (20 °C). In acetone 270, dichloromethane 300, toluene 220, methanol 190, n-octanol 130, hexane 9 (all in g/l, 20 °C). Stability Stable in neutral and alkaline media, but hydrolysed in strongly acidic media; DT 50 24–28 d (pH 1, 25 °C), >2.5 y (7<pH<13). Decomposed by uv light. COMMERCIALISATION: History Herbicide reported by G. A. Buchanan & D. L. Thurlow (Ala. Agr. Exp. Sta. Highlights, 1968, 15(2), 7). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). Patents CH 337019; GB 814948 APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective systemic herbicide, absorbed by the roots and foliage, with rapid translocation acropetally through the xylem, accumulating in the apical meristems and leaf tips. Uses Pre-emergence control of annual broad-leaved weeds and grasses in cotton and water melons at 1.25–3.5 kg/ha. Formulation types FW; SC. WP. PRODUCTS: Discontinued products ‘Cotofor’* (Ciba-Geigy); ‘Sancap’* (Ciba-Geigy). ANALYSIS: Product analysis by glc or by titration with perchloric acid in acetic acid. Residues determined by glc with FPD (B. G. Tweedy & R. A. Kahrs, Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 493; K. Ramsteiner et al., J. Assoc. Off. Anal. Chem., 1974, 57, 192). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3900–4200 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >10 000 mg/kg. Mild skin irritant; non-irritating to eyes (rabbits). No skin N N N CH 3 CH 2 S NHCH(CH 3 ) 2 NHCH(CH 3 ) 2 Supplementary Entries – Extended disul; disul-sodium 217 sensitisation (guinea pigs). NOEL (98 d) for rats 400 mg/kg diet (27 mg/kg daily); (133 d) for dogs 400 mg/kg diet (13 mg/kg daily). Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Practically non-toxic to birds. Fish LC 50 (96 h) for rainbow trout 2.7, bluegill sunfsh 1.6 mg/l. Bees Practically non-toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Degradation involves dealkylation of the side-chains, splitting of the ring, and evolution of CO 2 . Soil DT 50 c. 100 d. dipyrithione Fungicide NOMENCLATURE: Common name dipyrithione (BSI, E-ISO, (f) F-ISO, RINN) IUPAC name di-2-pyridyl disulfde 1,1′-dioxide Chemical Abstracts name 2,2′-dithiobis[pyridine] 1,1′-dioxide CAS RN [3696–28–4] Development codes OSY-20 Smiles code O=n1ccccc1SSc2ccccn2=O PHYSICAL CHEMISTRY: Mol. wt. 252.3 M.f. C 10 H 8 N 2 O 2 S 2 COMMERCIALISATION: History Fungicide and bactericide discovered by Olin Chemicals and developed by Yashima Chemical Industry Co. Ltd and Sankyo Co., Ltd. APPLICATIONS: Uses Developed as a fungicide for use in rice. PRODUCTS: Discontinued products ‘Omadine’* (Yashima); ‘Omadine disulfde’* (Yashima); ‘Omadine DS’* (Yashima). disul; disul-sodium Herbicide NOMENCLATURE: Common name sesone (WSSA); disul (E-ISO, (m) F-ISO); 2,4-DES (BSI, Australia, USSR) IUPAC name 2-(2,4-dichlorophenoxy)ethyl hydrogen sulfate (I) N S S N O O 218 The Pesticide Manual Sixteenth Edition © BCPC 2012 ditalimfos Chemical Abstracts name (I) Other names SES CAS RN [149–26–8] disul; [136– 78–7] disul-sodium EC no 205–259–5 disul PHYSICAL CHEMISTRY: Mol. wt. 287.1; (sodium salt 309.1) M.f. C 8 H 8 Cl 2 O 5 S; (sodium salt C8H7Cl 2 NaO5S) Form The sodium salt forms colourless crystals. M.p. 170 °C (sodium salt) V.p. Negligible (sodium salt, room temperature) Solubility In water 250 g/kg (sodium salt). Insoluble in most organic solvents except methanol. The calcium salt is suffciently soluble to avoid precipitation from solutions of 2,4-DES in hard water. Stability 2,4-DES-sodium is hydrolysed by alkali to form 2-(2,4-dichlorophenoxy)ethanol and sodium sulfate. COMMERCIALISATION: History Herbicide reported by L. J. King et al. (Contrib. Boyce Thompson Inst., 1950, 16, 191). Introduced by Union Carbide Corp. (later Rhône-Poulenc Ag.). Patents US 2573769 APPLICATIONS: Biochemistry 2,4-DES-sodium is not itself phytotoxic, but is converted in moist soil to 2-(2,4-dichlorophenoxy)ethanol which is oxidised to 2,4-D. Uses It was used as a mixture with simazine to control annual weeds pre-em. in maize, soft fruits, roses, certain established perennial crops and certain ornamental trees and shrubs. Formulation types WP. PRODUCTS: Discontinued products ‘Crag Herbicide I’* (disul) (Rhône-Poulenc); ‘Crag Sesone’* (disul) (Rhône-Poulenc); ‘Herbon’* (sodium salt) (Atlas Interlates); Discontinued mixtures ‘Herbon Blue’* (+ simazine) (Atlas). ANALYSIS: ANALYSIS: is by colorimetry of a derivative (J. N. Hogsett & G. L. Funk, Anal. Chem., 1954, 26, 849). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.142 (disul-sodium; 1995). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 730 mg/kg. NOEL In 2 y trials, rats receiving 2000 mg/kg diet suffered no ill-effect. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| Xi; R38, R41 (disul) ditalimfos Fungicide NOMENCLATURE: Common name ditalimphos ((m) F-ISO); ditalimfos (BSI, E-ISO, ANSI) IUPAC name O,O-diethyl phthalimidophosphonothioate; N-diethoxyphosphinothioylphthalimide Supplementary Entries – Extended ditalimfos 219 Chemical Abstracts name O,O-diethyl (1,3-dihydro-1,3-dioxo-2H- isoindol-2-yl)phosphonothioate CAS RN [5131–24–8] EC no 225–875–8 Development codes Dowco 199 Smiles code CCOP(=S)(OCC)N1C(=O) c2ccccc2C1=O PHYSICAL CHEMISTRY: Mol. wt. 299.3 M.f. C 12 H 14 NO 4 PS Form Colourless plates with a mild thiophosphate odour. M.p. 83–84 °C V.p. 1.93 × 10 –1 mPa (25 °C) Solubility In water c. 133 mg/l (room temperature). Soluble in hexane, cyclohexane, ethanol; very soluble in benzene, carbon tetrachloride, ethyl acetate and xylene. Stability Stable to uv light; its stability is reduced at pH >8 or above its m.p. No indication during storage of thiono-thiolo isomerisation which is characteristic of some phosphorothioate esters. COMMERCIALISATION: History Fungicide reported by H. Tolkmith (Nature (London), 1966, 211, 522). Introduced by Dow Chemical Co. (later DowElanco). Patents BE 661891, GB 1034493. APPLICATIONS: Mode of action Non-systemic foliar fungicide with protectant and curative activity. Uses For control of powdery mildew on ornamentals (primarily roses) and vegetables (cucurbits) under glass, as well as under feld conditions, at 30–50 g/100 l; on apples, at 25–5- g/100 l; and cereals,at 500–550 g/ha. Also used against Venturia inaequalis on apples at 37.5–100 g/100 l. Phytotoxicity Liable to russet certain apple cultivars, particularly Golden Delicious. Compatibility Not compatible with alkaline materials. PRODUCTS: Discontinued products ‘Plondrel’* (DowElanco). ANALYSIS: Product analysis is by uv spectroscopy. Residues by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 4930–5660, male guinea pigs 5660 mg/kg. Skin and eye Skin irritant; allergenic. Toxicity Class WHO (a.i.) U EC Classifcation Xi; R38| R43 ECOTOXICOLOGY: Birds Acute oral LD 50 for chickens 4500 mg/kg. 220 The Pesticide Manual Sixteenth Edition © BCPC 2012 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate dithicrofos Insecticide IRAC 1B NOMENCLATURE: Common name dithicrofos (BSI, E-ISO, (m) F-ISO) IUPAC name S-(6-chloro-3,4-dihydro-2H-1-benzothi-in-4-yl) O,O-diethyl phosphorodithioate Chemical Abstracts name S-(6-chloro-3,4-dihydro-2H-1-benzothiopyran-4-yl) O,O-diethyl phosphorodithioate CAS RN [41219–31–2] unstated stereochemistry Development codes Hoe 19 510 Smiles code CCOP(=S)(OCC)SC1CCSc2ccc(Cl) cc12 PHYSICAL CHEMISTRY: Mol. wt. 368.9 M.f. C 13 H 18 ClO 2 PS 3 COMMERCIALISATION: History Insecticide evaluated by Hoechst AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate Insecticide NOMENCLATURE: IUPAC name 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (I) Chemical Abstracts name (I) CAS RN [21709–44–4] Development codes C 13 963 Smiles code CN(C)C(=O)Oc1ccccc1C2SCCS2 PHYSICAL CHEMISTRY: Mol. wt. 269.4 M.f. C 12 H 15 NO 2 S 2 COMMERCIALISATION: History Insecticide reported by F. Bachmann & J. B. Legge (J. Sci. Food Agric., Suppl., 1968, p. 39). Evaluated by Ciba AG (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. Supplementary Entries – Extended DMCP 221 DKA-24 Herbicide safener NOMENCLATURE: IUPAC name N1,N 2 -diallyl-N 2 -dichloroacetylglycinamide Chemical Abstracts name 2,2-dichloro-N-[2-oxo-2-(2-propenylamino)ethyl]-N-2- propenylacetamide CAS RN [97454–00–7] Development codes DKA-24 (ÉMV) Smiles code ClC(Cl)C(=O)N(CC=C)CC(=O)NCC=C PHYSICAL CHEMISTRY: Mol. wt. 265.1 M.f. C 10 H 14 Cl 2 N 2 O 2 Form Pale yellow liquid. K ow logP = 1 Solubility In water 24.2 g/l (20 °C). In acetone, chloroform, DMF >200 g/l. Stability Stable ≤140 °C, and between pH 4.5 and 8.3. COMMERCIALISATION: History Herbicide safener reported by J. Nagy & K. Balogh (Proc. Br. Crop Prot. Conf. – Weeds, 1985, 1, 107). Introduced by Északmagyarországi Vegyimüvek Chemical Works, North Hungary (later SagroChem Co., Ltd). Patents HU 2143821 APPLICATIONS: Uses A safener at 200–1000 g/ha for thiocarbamate or 2-chloroacetanilide herbicides on maize. Formulation types EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2500–2520, male mice 1010, female mice 1660 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Non-irritating to eyes and skin. DMCP Insecticide NOMENCLATURE: Common name DMCP (JMAF) IUPAC name S-(4-chlorophenyl) O,O-dimethyl phosphorothioate C N CH 2 O NH C O HCCl 2 CH 2 =CHCH 2 CH 2 CH=CH 2 S(4-chlorophenyl) O,O-dimethyl phosphorothioate P O O O S Cl S(4-chlorophenyl) O,O-dimethyl phosphorothioate 222 The Pesticide Manual Sixteenth Edition © BCPC 2012 dodicin CAS RN [3309–87–3] Development codes B-3242 PHYSICAL CHEMISTRY: Mol. wt. 252.7 M.f. C 8 H 10 ClO 3 PS COMMERCIALISATION: History Insecticide marketed by Kumiai Chemical Industry Co. Ltd. PRODUCTS: Discontinued products ‘Fujithion’* (Kumiai). DMPA Herbicide NOMENCLATURE: Common name DMPA (WSSA) IUPAC name O-2,4-dichlorophenyl O-methyl isopropylphosphoramidothioate Chemical Abstracts name O-(2,4-dichlorophenyl) O-methyl (1-methylethyl) phosphoramidothioate CAS RN [299–85–4] Development codes K 22 023; Dowco 118 Smiles code COP(=S)(NC(C)C)Oc1ccc(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 314.2 M.f. C 10 H 14 Cl 2 NO 2 PS COMMERCIALISATION: History Herbicide introduced by Dow Chemical Co. (later DowElanco). PRODUCTS: Discontinued products ‘Zytron’* (DowElanco). dodicin Fungicide NOMENCLATURE: Common name dodicin (BSI, E-ISO, (f) F-ISO, BAN) IUPAC name N-[2-(2-dodecylaminoethylamino)ethyl]glycine; 3,6,9-triazahenicosanoic acid Chemical Abstracts name N-[2-[[2-(dodecylamino)ethyl]amino]ethyl]glycine CAS RN [6843–97–6] Smiles code CCCCCCCCCCCCNCCNCCNCC(=O)O PHYSICAL CHEMISTRY: Mol. wt. 329.5 M.f. C 18 H 39 N 3 O 2 COMMERCIALISATION: History Fungicide and surface active agent. Supplementary Entries – Extended drazoxolon 223 dofenapyn Acaricide NOMENCLATURE: Common name dofé(napyne) ((m) F-ISO); dofenapyn (BSI, E-ISO) IUPAC name 4-(pent-4-ynyloxy)phenyl phenyl ether Chemical Abstracts name 1-(4-pentynyloxy)-4-phenoxybenzene AS RN [42873–80–3] Development codes CGA 29 170 Smiles code C#CCCCOc1ccc(Oc2ccccc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 252.3 M.f. C 17 H 16 O 2 COMMERCIALISATION: History Acaricide discovered by Ciba-Geigy AG. PRODUCTS: Discontinued products ‘Acaban’* (Ciba). drazoxolon Fungicide NOMENCLATURE: Common name drazoxolon (BSI, E-ISO, (m) F-ISO) IUPAC name 4-(2-chlorophenylhydrazono)-3-methyl-1,2-oxazol-5(4H)-one; 4-(2-chlorophenylhydrazono)-3-methylisoxazol-5(4H)-one Chemical Abstracts name 3-methyl-4,5-isoxazoledione 4-[(2-chlorophenyl) hydrazone] CAS RN [5707–69–7] EC no 227–197–8 Development codes PP781 Smiles code CC1=NOC(=O)C1=NNc2ccccc2Cl PHYSICAL CHEMISTRY: Mol. wt. 237.6 M.f. C 10 H 8 ClN 3 O 2 Form Yellow crystals. M.p. 167 °C V.p. 0.53 mPa (30 °C) K ow logP = 2.6 Solubility In water <10 g/l (20 °C).In ethanol 10, chloroform 100, ketones 50, aromatic hydrocarbons 40 (all in g/kg). Practically insoluble in acids and aliphatic hydrocarbons. Stability Stable in storage under normal conditions. Stable to acids; dissolves in aqueous alkalis to form stable, soluble salts. COMMERCIALISATION: History Fungicide reported by M. J. Geoghegan (Proc. Br. Insectic. Fungic. Conf., 4th, 1967, 1, 451). Introduced by ICI Plant Protection Division (later Zeneca Agrochemicals). Patents GB 999097 Cl O CH 3 N O N NH 224 The Pesticide Manual Sixteenth Edition © BCPC 2012 DSP APPLICATIONS: Mode of action Foliar fungicide and seed treatment with protective and curative action. Uses Control of powdery mildews on roses, blackcurrants, and other crops; coffee rust; tea blister blight; Ganoderma spp. on rubber trees; etc. Also seed treatment for control of Pythium and Fusarium spp. in peas, beans, peanuts, maize, cotton, and grass. Phytotoxicity Mixtures with dodine are phytotoxic to apples. Formulation types SC. FS . Compatibility Incompatible with lime sulfur. PRODUCTS: Discontinued products ‘Ganocide’* (ICI); ‘Mil-Col’* (Zeneca); ‘SAIsan’* (ICI). ANALYSIS: Product and residue analysis by colorimetry (S. H. Yuen, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 665). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 126, mice 129, rabbits 100–120, guinea pigs 12.5–25, dogs 17, cats 50–100 mg/kg. Skin and eye Non-irritating to skin and eyes, but some sensitisation may occur, and prolonged contact should be avoided. Inhalation Rats exposed to 0.004 mg/l air for 15 daily periods of 6 h showed no toxic effect. Causes some lung irritation; avoid vapour concentrations >0.0005 mg/l air. NOEL In 90 d feeding trials, rats receiving 30 mg/kg diet showed no ill-effects. Toxicity Class WHO (a.i.) II EC Classifcation T; R25| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for hensc. 100 mg/kg. Fish LC 50 (96 h) for brown trout 0.55 mg/l. DSP Insecticide IRAC 1B NOMENCLATURE: Common name DSP (JMAF) IUPAC name O-4-dimethylsulfamoylphenyl O,O-diethyl phosphorothioate; 4-diethoxyphosphinothioyloxy-N,N-dimethylbenzenesulfonamide Chemical Abstracts name O-[4-[(dimethylamino)sulfonyl]phenyl] O,O-diethyl phosphorothioate CAS RN [3078–97–5] Development codes NK 0795 Smiles code CCOP(=S)(OCC)Oc1ccc(cc1)S(=O)(=O)N(C)C PHYSICAL CHEMISTRY: Mol. wt. 353.4 M.f. C 12 H 20 NO 5 PS 2 COMMERCIALISATION: History Insecticide introduced by Nippon Soda Co., Ltd. Supplementary Entries – Extended eglinazine-ethyl; eglinazine 225 APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Kayaace’* (Nippon Soda). EBP Fungicide IRAC 1B NOMENCLATURE: Common name EBP (JMAF) IUPAC name S-benzyl O,O-diethyl phosphorothioate Chemical Abstracts name O,O-diethyl S-(phenylmethyl) phosphorothioate CAS RN [13286–32–3] Smiles code CCOP(=O)(OCC)SCc1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 260.3 M.f. C 11 H 17 O 3 PS COMMERCIALISATION: History Fungicide introduced by Kumiai Chemical Industry Co., Ltd. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Kitazin’* (Kumiai). eglinazine-ethyl; eglinazine Herbicide NOMENCLATURE: Common name eglinazine (for acid) (BSI, E-ISO, (f) F-ISO, WSSA) IUPAC name N-(4-chloro-6-ethylamino-1,3,5-triazin-2-yl)glycine (for acid) Chemical Abstracts name N-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]glycine (for acid) CAS RN [6616–80–4] ester; [68228–19–3] acid Development codes MG-06 (ester) N N N Cl NHCH 2 CO 2 H CH 3 CH 2 NH 226 The Pesticide Manual Sixteenth Edition © BCPC 2012 EI 1642 PHYSICAL CHEMISTRY: Composition Tech. isc. 96%. Mol. wt. 259.7; (acid 231.6) M.f. C 9 H 14 ClN 5 O 2 (ester); C7H 10 ClN5O 2 (acid) Form Colourless crystals (ester). M.p. 228–230 °C (ester) V.p. 0.027 mPa (20 °C) (ester) Solubility In water 300 mg/l (25 °C) (ester). In acetone 200, hexane 20, xylene 40 (all in g/l, 25 °C) (ester). Stability Stable at room temperature at pH 5–8. Hydrolysed on heating with acids or alkalis, forming the hydroxytriazine (which is herbicidally inactive). Stable to light. Decomposes at 250 °C. COMMERCIALISATION: History The ethyl ester introduced as a herbicide by Nitrokémia Ipartelepek. APPLICATIONS: Uses Eglinazine-ethyl was used pre-emergence for control of loose silky-bent (Apera spica-venti) and scentless mayweed (Matricaria perforata) in cereals at 3 kg/ha. Formulation types WP. PRODUCTS: Discontinued products ‘MG06’* (Nitrokémia). ANALYSIS: Product analysis by glc. Residues determined by glc with TID. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >10 000, guinea pigs >3375 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and rabbits >10 000 mg/kg. Non-irritating to skin and eyes. Other Acute i.p. LD 50 for rats and mice >7100 mg/kg. No evidence of cumulative toxicity. Toxicity Class WHO (a.i.) U ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 c. 12–18 d. EI 1642 Insecticide NOMENCLATURE: IUPAC name S-methyl N-(carbamoyloxy)thioacetimidate Chemical Abstracts name methyl N-[(aminocarbonyl)oxy]ethanimidothioate CAS RN [16960–39–7] Development codes EI 1642 Smiles code CSC(=NOC(=O)N)C PHYSICAL CHEMISTRY: Mol. wt. 148.2 M.f. C 4 H 8 N 2 O 2 S Form Colourless crystals. M.p. 103–104 °C Solubility In water 45 g/kg (25 °C). In acetone 170, ethanol 100, methanol 300, isopropanol 30 (all in g/kg, 25 °C); practically insoluble in kerosine, toluene. COMMERCIALISATION: History Insecticide evaluated by E. I. du Pont de Nemours & Co. Supplementary Entries – Extended EL 177 227 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses Effective as a foliar spray (150–300 mg/l) against aphids, lepidopterous and many other insect pests. Formulation types WP. MAMMALIAN TOXICOLOGY: Oral The oral lethal dose for male rats isc. 60 mg/kg. Skin and eye Percutaneous lethal dose for rabbits is >3400 mg/kg; it is not a skin irritant. NOEL In a 14 d trial with rats, ten doses of 12 mg/kg showed no cumulative toxicity. EL 177 Herbicide NOMENCLATURE: IUPAC name 1-tert-butyl-5-cyano-N-methylpyrazole-4-carboxamide Chemical Abstracts name 5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H-pyrazole- 4-carboxamide CAS RN [98477–07–7] Development codes EL-177; LYI 81 977 Smiles code CNC(=O)c1cnn(c1C#N)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 206.2 M.f. C 10 H 14 N 4 O Form Crystalline solid. M.p. 164–166 °C K ow logP = 1.3 Solubility Readily soluble in acetone, DMSO. Stability Stable to light; and to hydrolysis at pH 3 and pH 7, slowly hydrolysed at pH 11. COMMERCIALISATION: History Herbicide reported by H. E. Chamberlain et al. (Proc. 1987 Br. Crop Prot. Conf. - Weeds, 1, 35). Introduced by Eli Lilly. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice and male rats >500 mg tech./kg, for female rats >50 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Not a skin irritant; slight eye irritant (rabbits). NOEL (42 d) for female rats 57 mg/kg daily, slight increase in liver enzyme activity in males. Other Not teratogenic in rats at 250 mg/kg daily (highest dose tested). Not mutagenic or genotoxic in Ames assay. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail >500 mg/kg. Fish LC 50 (96 h) for bluegill sunfsh >100 mg/l, rainbow trout >62 mg/l. ENVIRONMENTAL FATE: Soil/Environment Soil/water distribution coeffcient 0.31 (coarse-), 0.4 (medium-) and 0.45 (fne-textured soil). 228 The Pesticide Manual Sixteenth Edition © BCPC 2012 endothion EMPC Insecticide NOMENCLATURE: Common name EMPC (JMAF) IUPAC name 4-ethylthiophenyl methylcarbamate Chemical Abstracts name 4-(ethylthio)phenyl methylcarbamate CAS RN [18809–57–9] Development codes NK-1 Smiles code CCSc1ccc(OC(=O)NC)cc1 PHYSICAL CHEMISTRY: Mol. wt. 211.3 M.f. C 10 H 13 NO 2 S COMMERCIALISATION: History Insecticide introduced by Nippon Kayaku Co., Ltd. Registration in Japan cancelled in 1974. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Toxamate’* (Nippon Kayaku). endothion Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name endothion (BSI, E-ISO, (m) F-ISO, ESA, ex ANSI) IUPAC name S-5-methoxy-4-oxo-4H-pyran-2-ylmethyl O,O-dimethyl phosphorothioate; 2-dimethoxyphosphinoylthiomethyl-5-methoxypyran-4-one Chemical Abstracts name S-[(5-methoxy-4-oxo-4H-pyran-2-yl)methyl] O,O-dimethyl phosphorothioate CAS RN [2778–04–3] EC no 220–472–3 Development codes 7175 RP (Rhône-Poulenc); AC 18 737 (Cyanamid); FMC 5767 (FMC) Smiles code COc1coc(CSP(=O)(OC)OC)cc1=O PHYSICAL CHEMISTRY: Mol. wt. 280.2 M.f. C 9 H 13 O 6 PS COMMERCIALISATION: History Insecticide reported by F. Chaboussou & P. Ramadier (Rev. Zool. Agric. Appl., 1957, 55, 116). Introduced by Rhône-Poulenc Phytosanitaire and later by American Cyanamid Co. and FMC Corp. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Endocide’* (Rhône-Poulenc). Supplementary Entries – Extended endrin 229 MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T; R24/25 endrin Insecticide NOMENCLATURE: Common name nendrin (Republic of South Africa); endrine ((f) F-ISO); endrin (BSI, E-ISO, ESA, JMAF) IUPAC name (1R,4S,4aS,5S,6S,7R,8R,8aR)-1,2,3,4,10,10-hexachloro-1,4,4a,5,6,7,8,8a- octahydro-6,7-epoxy-1,4:5,8-dimethanonaphthalene Chemical Abstracts name (1aα,2β,2aβ,3α,6α,6aβ,7β,7aα)-3,4,5,6,9,9-hexachloro- 1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-dimethanonaphth[2,3-b]oxirene CAS RN [72–20–8] EC no 200–775–7 Development codes Experimental Insecticide 269 (Hyman) Smiles code ClC1=C(Cl)C2(Cl)C3C4CC(C5OC54)C3C1(Cl)C2(Cl)Cl PHYSICAL CHEMISTRY: Composition Tech. is ≥92%. Mol. wt. 380.9 M.f. C 12 H 8 Cl 6 O Form Colourless crystalline solid; (tech. is a light tan solid). M.p. 226–230 °C (decomp.); (tech >200 °C, decomp.) V.p. 2 × 10 –5 mPa (20 °C) S.g./density 1.64 (20 °C) Solubility Negligible in water. Moderately soluble in acetone, benzene; sparingly in alcohols, petroleum hydrocarbons. Stability Tech. decomposes >200 °C. COMMERCIALISATION: History Developed by Shell International Chemical Co. after introduction by J. Hyman & Co. Patents US 2676132 APPLICATIONS: Mode of action Contact insecticide. Uses Endrin is a foliar insecticide which acts against a wide range of pests particularly Lepidoptera. It was used at 0.2–0.5 kg/ha on cotton, maize, sugar cane, upland rice and many other crops. Formulation types EC; GR; WP. PRODUCTS: Discontinued products ‘Endrex’* (Shell); ‘Mendrin’* (Shell); ‘Nendrin’* (Velsicol). ANALYSIS: Product analysis by i.r. spectroscopy (CIPAC Handbook, 1983, 1B, 1805; FAO Specifcation (CP/46); AOAC Methods 18th Ed., 961.05; Organochlorine Insecticides 1973), by tlc (AOAC Methods 18th Ed., 972.05), or by potentiometric titration of liberated chloride ion (CIPAC Handbook, 1994, F, 190), or by glc; mixtures with DDT and with parathion-methyl by i.r. spectroscopy (CIPAC Handbook, 1983, 1B, 1760, 1819). Residues determined by glc, tlc or paper chromatography (AOAC Methods, 18th Ed., 970.52), or by glc with ECD (Analyst (London), 1979, 104, 425; G. M. Telling et al., J. Chromatogr., 1977, 137, 405; M. A. Luke et al., J. 230 The Pesticide Manual Sixteenth Edition © BCPC 2012 enoxastrobin Assoc. Off. Anal. Chem., 1981, 64, 1187; A. Ambrus et al., ibid., p. 733; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 0393). In drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). See also Pestic. Anal. Man., I, 204, 208, 301, 302, 303, 502. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 130 (1992). JMPR Mtg. 65 (1992); JMPR Evaln. 25 (1975). HSG 60 (1991). PDS 1 (1975). ICSC.023 (2000). IARC 5 (1974). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EC, as amended by Regulation 850/2004. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for rats 7.5–17.5 mg/kg. Skin and eye Acute percutaneous LD 50 for female rats 15 mg/kg. NOEL (2 y) for rats and dogs 1 mg/kg diet (0.025 mg/kg b.w. for dogs); rats and mice showed no carcinogenic response. ADI/RfD (JMPR) 0.0002 mg/ kg b.w. (PTDI) [1994]; (EPA) cRfD 0.0003 mg/kg b.w. [1991]. Water GV 0.6 μ;g/l Other Produces neurotoxic effects. Toxicity Class WHO (a.i.) Ib EC Classifcation T+; R28| T; R24| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for birds 0.75–5.64 mg/kg. Fish LC 50 (24 h) for fsh 0.75–5.6 mg/l. ENVIRONMENTAL FATE: Animals It is rapidly metabolised in animals to hydrophilic metabolites which are excreted (M. R. Baldwin et al., Pestic. Sci., 1976, 7, 575). Continuous exposure to endrin in diets results in only a limited accumulation in body fat. enoxastrobin Fungicide NOMENCLATURE: Common name enoxastrobin (pa ISO) IUPAC name methyl 2-{2-[({[3-(4-chlorophenyl)-1-methylprop-2-enylidene]amino}oxy) methyl]phenyl}-3-methoxyacrylate Chemical Abstracts name methyl 2-[[[[3-(4-chlorophenyl)-1-methyl-2-propen-1- ylidene]amino]oxy]methyl]-α-(methoxymethylene)benzeneaceate CAS RN [238410–11–2] Development codes SYP–Z071 Smiles code C\C(/C=C/ C1=CC=C(Cl)C=C1)=N/OCC2=CC=CC=C2/C(C(OC)=O)=C\OC PHYSICAL CHEMISTRY: Mol. wt. 399.9 M.f. C 22 H 22 ClNO 4 O N CH 3 Cl CO 2 Me O H 3 C Supplementary Entries – Extended epofenonane 231 EPBP Insecticide IRAC 1B NOMENCLATURE: Common name EPBP (JMAF) IUPAC name O-2,4-dichlorophenyl O-ethyl phenylphosphonothioate Chemical Abstracts name O-(2,4-dichlorophenyl) O-ethyl phenylphosphonothioate CAS RN [3792–59–4] Development codes S-7 (Nissan) Smiles code CCOP(=S)(Oc1ccc(Cl)cc1Cl)c2ccccc2 PHYSICAL CHEMISTRY: Composition Tech. isc. 90%. Mol. wt. 347.2 M.f. C 14 H 13 Cl 2 O 2 PS Form Light brown oil. B.p. 206 °C /5 mmHg V.p. 5.09 × 10 5 mPa (200 °C) S.g./density 1.312 (24 °C) Solubility Practically insoluble in water; soluble in most organic solvents. COMMERCIALISATION: History Insecticide introduced by Nissan Chemical Industries Ltd. Patents US 3318764 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact and ingested insecticide. Uses Used mainly to control soil-dwelling pests such as Agrotis fucosa, Phyllotreta striolata, Rhizoglyphus echinopus and Hylemya spp. etc., using the dust at 1.8–3.0 kg/ha. Formulation types DP . PRODUCTS: Discontinued products ‘S7’* (Nissan); ‘SSeven’* (Nissan). ANALYSIS: Product analysis by glc. Residues determined by glc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice 275 mg/kg. Toxicity Class WHO (a.i.) II epofenonane Insecticide NOMENCLATURE: Common name epofenonane (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name 6,7-epoxy-3-ethyl-7-methylnonyl 4-ethylphenyl ether Chemical Abstracts name 2-ethyl-3-[3-ethyl-5-(4-ethylphenoxy)pentyl]-2- methyloxirane CAS RN [57342–02–6] Development codes Ro 10–3108 Smiles code CCC(CCOc1ccc(CC)cc1)CCC2OC2(C)CC PHYSICAL CHEMISTRY: Mol. wt. 304.5 M.f. C 20 H 32 O 2 232 The Pesticide Manual Sixteenth Edition © BCPC 2012 erbon COMMERCIALISATION: History Insect growth regulator evaluated by Hoffmann-La Roche & Co. epronaz Herbicide NOMENCLATURE: Common name epronaz (BSI, E-ISO, (m) F-ISO) IUPAC name N-ethyl-N-propyl-3-propylsulfonyl-1H-1,2,4-triazole-1-carboxamide Chemical Abstracts name N-ethyl-N-propyl-3-(propylsulfonyl)-1H-1,2,4-triazole- 1-carboxamide CAS RN [59026–08–3] Development codes BTS 30 843 Smiles code CCCN(CC)C(=O)n1cnc(n1)S(=O)(=O)CCC PHYSICAL CHEMISTRY: Mol. wt. 288.4 M.f. C 11 H 20 N 4 O 3 S COMMERCIALISATION: History Herbicide reported by L. G. Copping & R. F. Brookes (Proc. Br. Weed Control Conf., 12th, 1974, 2, 809). Evaluated by Boots Co., Ltd (later Schering Agriculture). erbon Herbicide NOMENCLATURE: Common name erbon (E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name 2-(2,4,5-trichlorophenoxy)ethyl 2,2-dichloropropionate Chemical Abstracts name 2-(2,4,5-trichlorophenoxy)ethyl 2,2-dichloropropanoate CAS RN [136–25–4] Smiles code CC(Cl)(Cl)C(=O)OCCOc1cc(Cl)c(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 366.5 M.f. C 11 H 9 Cl 5 O 3 COMMERCIALISATION: History Herbicide introduced by Dow Chemical Co. (later DowElanco). APPLICATIONS: Mode of action Total herbicide. PRODUCTS: Discontinued products ‘Daron’* (DowElanco). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22| N; R51, R53 Supplementary Entries – Extended etacelasil 233 ESBP Fungicide NOMENCLATURE: Common name ESBP (JMAF) IUPAC name S-benzyl O-ethyl phenylphosphonothioate Chemical Abstracts name O-ethyl S-(phenylmethyl) phenylphosphonothioate CAS RN [21722–85–0] Smiles code CCOP(=O)(SCc1ccccc1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 292.3 M.f. C 15 H 17 O 2 PS COMMERCIALISATION: History Fungicide introduced by Nissan Chemical Industries Ltd. PRODUCTS: Discontinued products ‘Inezin’* (Nissan). etacelasil Plant growth regulator NOMENCLATURE: Common name etacelasil (BSI, E-ISO, (m) F-ISO) IUPAC name 2-chloroethyltris(2-methoxyethoxy)silane Chemical Abstracts name 6-(2-chloroethyl)-6-(2-methoxyethoxy)-2,5,7,10-tetraoxa-6- silaundecane CAS RN [37894–46–5] EC no 253–704–7 Development codes CGA 13 586 Smiles code COCCO[Si](CCCl)(OCCOC)OCCOC PHYSICAL CHEMISTRY: Mol. wt. 316.9 M.f. C 11 H 25 ClO 6 Si Form Colourless liquid. B.p. 85 °C /0.001 mmHg V.p. 27 mPa (20 °C) Henry 3.42 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.10 (20 °C) Solubility In water 25 g/l (20 °C). Miscible with benzene, methanol, hexane, dichloromethane and n-octanol. Stability On hydrolysis, DT 50 (calc., 20 °C) 50 min (pH 5), 160 min (pH 6), 43 min (pH 7), 23 min (pH 8). COMMERCIALISATION: History Abscission agent reported by J. Rufener & D. Pietà (Riv. Ortoforofruttic. Ital., 1974, 4, 274). Introduced by Ciba-Geigy AG. Patents BE 773498; GB 1371804 APPLICATIONS: Mode of action Abscission agent which loosens fruit because of its ethylene-releasing activity. Uses Loosening of olive fruit, which were then removed by mechanical shaking. Formulation types SC. SL . Compatibility Not to be applied to trees recently sprayed with copper fungicides or other pesticides containing stickers or surfactants. PRODUCTS: Discontinued products ‘Alsol’* (Ciba-Geigy). 234 The Pesticide Manual Sixteenth Edition © BCPC 2012 etaconazole ANALYSIS: Product analysis by glc. Residues determined by glc with MCD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2066 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats >3100 mg/kg. Slight irritant to skin, not irritating to eyes (rabbits). Inhalation LC 50 (4 h) for rats >3.7 mg/l air. NOEL (90 d) for rats 20 mg/kg daily, for dogs 10 mg/kg daily. Toxicity Class WHO (a.i.) III EC Classifcation R61| Xn; R22, R48/22 ECOTOXICOLOGY: Birds Non-toxic to birds. Fish LC 50 (96 h) for rainbow trout, crucian carp, bluegill sunfsh >100 mg/l. etaconazole Fungicide FRAC 3, G1; SBI Class I, DMI: triazole NOMENCLATURE: Common name é(taconazole) ((m) F-ISO); etaconazole (BSI, E-ISO) IUPAC name (±)-1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4- triazole Chemical Abstracts name 1-[[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl] methyl]-1H-1,2,4-triazole CAS RN [60207–93–4] unstated stereochemistry, formerly [71245–23–3] Development codes CGA 64 251 Smiles code CCC1COC(Cn2cncn2)(O1)c3ccc(Cl)cc3Cl PHYSICAL CHEMISTRY: Mol. wt. 328.2 M.f. C 14 H 15 Cl 2 N 3 O 2 Form Colourless crystals. M.p. 75–93 °C (depending on ratio of stereoisomers) V.p. 0.031 mPa (20 °C) Henry 1.27 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.40 (20 °C) Solubility In water 80 mg/l (20 °C). In acetone 300, dichloromethane 700, hexane 7.5, methanol 400, isopropanol 100, toluene 250 (all in g/kg, 20 °C). Stability Stable to hydrolysis, and at <350 °C. COMMERCIALISATION: History Fungicide reported by T. Staub et al. (Abstr. Int. Congr. Plant Protect., 1979, p. 310). Introduced by Ciba-Geigy AG as an agricultural fungicide, having been invented by Janssen Pharmaceutica, N.V. Patents GB 1522657; BE 835579 APPLICATIONS: Biochemistry Sterol demethylation inhibitor. Mode of action Systemic, protective and curative fungicide. Uses Used against Ascomycetes, Basidiomycetes and Deuteromycetes; it has no activity on Oomycetes. It is especially active on powdery mildews, rusts, sclerotinia and Venturia spp. on various crops. Post-harvest treatments are active against Fungi Supplementary Entries – Extended etem 235 including Diplodia, Geotrichum and Penicillium spp. and others. (J. D. Van Geluwe et al., Abstr. Int. Congr. Plant Protect., 1979, 495; J. D. Gilpatrick, ibid., p. 312). Formulation types WP. PRODUCTS: Discontinued products ‘Sonax’* (Ciba-Geigy); ‘Vangard’* (Ciba-Geigy). ANALYSIS: Product analysis by glc with TID. Residues determined by glc with FID. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1343 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3100 mg/kg. Slight skin and eye irritant (rabbits). Toxicity Class WHO (a.i.) III etem Fungicide An oxidation product of nabam (q.v.) (C. W. Pluijgers et al., Tetrahedron Lett., 1971, 1371; W. R. Benson et al., J. Assoc. Off. Anal. Chem., 1972, 55, 44; M. Alvarez et al., Tetrahedron Lett., 1973, 939). Also identifed as one of the oxidation products of other ethylenebis(dithiocarbamates), e.g. maneb and zineb (R. A. Ludwig et al., Can. J. Bot., 1955, 33, 42). NOMENCLATURE: Common name ETM for (ii) (JMAF); etem for (i) (BSI); etem* for (ii) (BSI, before 1974) IUPAC name (i) 5,6-dihydro-[3H]-imidazo[2,1-c]-[1,2,4]-dithiazole-3-thione; (ii) 1,3,6-thiadiazepane-2,7-dithione; ethylenethiuram monosulfde Chemical Abstracts name (i) 5,6-dihydro-3H-imidazo[2,1-c]-1,2,4-dithiazole-3-thione; (ii) hexahydro-1,3,6-thiadiazepine-2,7-dithione CAS RN [33813–20–6] (i); [5782–83–2] (ii) EC no 251–684–4 Development codes UCP/21 PHYSICAL CHEMISTRY: Composition Tech. may be contaminated by sulfur. Mol. wt. 176.3 (i); 178.3 (ii) M.f. C 4 H 4 N 2 S 3 (i); C 4 H 6 N 2 S 3 (ii) Form Yellow crystalline powder. M.p. 121–124 °C COMMERCIALISATION: History Fungicide originally believed to be (ii), later corrected to (i). Evaluated by Universal Crop Protection Ltd. PRODUCTS: Discontinued products ‘Vegita’* (Hokko, Kumiai). S S N N S 236 The Pesticide Manual Sixteenth Edition © BCPC 2012 ethidimuron ANALYSIS: Residue analysis is by glc (W. H. Newsome, J. Agric. Food Chem., 1975, 23, 348) or by polarography (R. Engst & W. Schnaak, Z. Lebensm.-Unters. -Forsch., 1970, 144, 81). MAMMALIAN TOXICOLOGY: EC Classifcation Xn; R22| N; R50, R53 ethidimuron Herbicide HRAC C2 WSSA 7; urea NOMENCLATURE: Common name ethidimuron (BSI, E-ISO, (m) F-ISO) IUPAC name 1-(5-ethylsulfonyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea Chemical Abstracts name N-[5-(ethylsulfonyl)-1,3,4-thiadiazol-2-yl]-N,N′- dimethylurea Other names sulfodiazol CAS RN [30043–49–3] EC no 250–010–6 Development codes MET 1486; BAY 107033 Smiles code CCS(=O)(=O)c1nnc(s1)N(C)C(=O)NC PHYSICAL CHEMISTRY: Mol. wt. 264.3 M.f. C 7 H 12 N 4 O 3 S 2 Form Colourless crystals. M.p. 155.9–156 °C B.p. Decomposes on distillation V.p. 8 × 10 –5 mPa (20 °C) K ow logP = 0.43 Henry 7.05 × 10-9 Pa m 3 mol –1 (calc.) Solubility In water 3 g/l (20 °C). In hexane <0.1, toluene 0.1–1.0, methanol 2, isopropanol 6, dichloromethane 106, chloroform 108, acetone 150, acetonitrile 240 (all in g/kg, 20 °C). Stability Stable in aqueous neutral and acidic media, but unstable in alkaline media. Decomposes at 217 °C. COMMERCIALISATION: History Herbicide reported by L. Eue et al. (C. R. Journ. Etud. Herbic. Conf. COLUMA, 4th, 1973, 1, 14). Introduced by Bayer AG. Patents BE 743615 APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Non-selective herbicide, absorbed predominantly by the roots. Uses Total herbicidal control on uncultivated land at 7 kg/ha, and in sugar cane plantations. Formulation types WP; SC. PRODUCTS: Discontinued products ‘Ustilan’* (Bayer); Discontinued mixtures ‘Novorail’* (+ amitrole + diuron) (CFPI). N N S SO 2 CH 2 CH 3 N C CH 3 NH O CH 3 Supplementary Entries – Extended ethiolate 237 ANALYSIS: Product analysis by i.r. spectrometry. Residues determined by glc with TID (H. J. Jarczyk, Pfanz.-Nachr. Bayer (Engl. Ed.), 1979, 32, 186). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000, mice >2500, male dogs >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg. Non-irritating to skin and eyes. Inhalation LC 50 (4 h) for rats, mice, and hamsters >0.24 mg/l air. NOEL (90 d) for rats >1000 mg/kg diet. Toxicity Class WHO (a.i.) U EPA (formulation) IV EC Classifcation R43| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for Japanese quail 300–400, canaries 1000 mg/kg. Fish LC 50 (96 h) for golden orfe >1000, goldfsh 400–500, carp 200–300 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 c. 3–4 months. ethiolate Herbicide NOMENCLATURE: Common name ethiolate (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name S-ethyl diethylthiocarbamate Chemical Abstracts name S-ethyl diethylcarbamothioate CAS RN [2941–55–1] Smiles code CCSC(=O)N(CC)CC PHYSICAL CHEMISTRY: Mol. wt. 161.3 M.f. C 7 H 15 NOS COMMERCIALISATION: History Herbicide introduced by Gulf Oil Chemicals Co. PRODUCTS: Discontinued mixtures ‘Prefox’* (+ cyprazine) (Gulf). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 76 (1988); a general review of thiocarbamates. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O 238 The Pesticide Manual Sixteenth Edition © BCPC 2012 ethirimol ethirimol Fungicide FRAC 8, A2 NOMENCLATURE: Common name ethirimol (BSI, E-ISO); é(thyrimol) ((m) F-ISO) IUPAC name 5-butyl-2-ethylamino-6-methylpyrimidin-4-ol Chemical Abstracts name 5-butyl-2-(ethylamino)-6-methyl-4(1H)-pyrimidinone (C.A. preferred tautomer) CAS RN [23947–60–6] EC no 245–949–3 Development codes PP149 (ICI) Smiles code CCCCc1c(C)nc(NCC)nc1O PHYSICAL CHEMISTRY: Composition Tech. material is 97% pure. Mol. wt. 209.3 M.f. C 11 H 19 N 3 O Form Colourless crystals. M.p. 159–160 °C (phase change atc. 140 °C) V.p. 0.267 mPa (25 °C) K ow logP = 2.3 (pH 7, 20 °C) Henry ≤2 × 10 –4 (pH 5.2); ≤4 × 10 –4 (pH 7.3); ≤4 × 10 –4 (pH 9.3) Pa m 3 mol –1 (20 °C) S.g./density 1.21 (25 °C) Solubility In water 253 (pH 5.2), 150 (pH 7.3), 153 (pH 9.3) (all in mg/l, 20 °C). In chloroform 150, ethanol 24, acetone 5 (all in g/kg, 20 °C). Stability Stable to heat, and in acidic and alkaline solutions in the dark. Aqueous solution exposed to sunlight and air had DT 50 c. 21 d. pKa 5, weak base (K. Chamberlain et al., Pestic. Sci., 1996, 47, 265 and ref. therein). COMMERCIALISATION: History Fungicide reported by R. M. Bebbington et al. (Chem. Ind. (London), 1969, p. 1512). Introduced by ICI Plant Protection Division (later Syngenta AG) and frst marketed in 1970. Patents GB 1182584 Manufacturers Syngenta; Zhejiang Heyi APPLICATIONS: Biochemistry Inhibits nucleic acid synthesis (adenosine deaminase). Mode of action Systemic fungicide with protective and curative action. Absorbed by the roots and leaves, with translocation in the xylem, but not in the phloem. Uses Control of powdery mildew on barley, wheat, and oats. Applied as a seed dressing, at 4 g/1000 g seed, a foliar spray, at 250–350 g/ha, or to the soil in the root zone. Also used for control of powdery mildews on cucurbits. Formulation types EC; LS; SC. PRODUCTS: Discontinued products ‘Milcurb Super’* (Zeneca); ‘Milgo’* (Zeneca); ‘Milstem’* (Zeneca); Discontinued mixtures ‘Ferrax’* (+ futriafol + thiabendazole) (seed) (Cheminova, Syngenta); ‘Halley’* (+ hexaconazole) (Zeneca). N N NHCH 2 CH 3 CH 3 CH 3 (CH 2 ) 3 OH Supplementary Entries – Extended ethoate-methyl 239 ANALYSIS: Product analysis by glc of a derivative (CIPAC Handbook, 1988, D, 72; J. E. Bagness & W. G. Sharples, Analyst (London), 1974, 99, 225). Residues in crops determined by glc and in water by hplc or by spectrometry (M. J. Edwards, Anal. Methods Pestic. Plant Growth Regul., 1976, 8, 285). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for female rats 6340, mice 4000, female guinea pigs 500–1000, male rabbits 1000–2000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Mild eye irritant; non-irritating to skin (rats). Not a skin sensitiser (guinea pigs). Inhalation LC 50 for rats >4.92 mg/l. NOEL (2 y) for rats 200 mg/kg diet, for dogs 30 mg/ kg daily. Not carcinogenic or teratogenic. ADI/RfD (BfR) 0.1 mg/kg b.w. [1989]; (EPA) 0.05 mg/kg b.w. Toxicity Class WHO (a.i.) U EPA (formulation) IV EC Classifcation Xn; R21 ECOTOXICOLOGY: Birds Acute oral LD 50 for hens 4000 mg/kg. Fish LC 50 (96 h) for young brown trout 20, rainbow trout 66 mg/l. Daphnia LC 50 (48 h) 53 mg/l. Bees LD 50 (oral) 1.6 mg/bee. ENVIRONMENTAL FATE: Animals In rats, following oral administration, metabolism involves hydroxylation of the butyl group. Elimination is in the urine. Plants In plants, ethirimol undergoes rapid degradation; 2-amino-5-butyl-6-hydroxy-4-methylpyrimidine is found as a metabolite. DT 50 in plantsc. 3 d. Soil/Environment Soil DT 50 14–140 d (o.m. 1.0–10.1%, pH 7.8–8.1). ethoate-methyl Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name ethoate-methyl (BSI, E-ISO); é(thoate-mé) (F-ISO) IUPAC name S-ethylcarbamoylmethyl O,O-dimethyl phosphorodithioate; 2-dimethoxyphosphinothioylthio-N-ethylacetamide Chemical Abstracts name S-[2-(ethylamino)-2-oxoethyl] O,O-dimethyl phosphorodithioate CAS RN [116–01–8] EC no 204–121–1 Development codes B/77 Smiles code CCNC(=O)CSP(=S)(OC)OC PHYSICAL CHEMISTRY: Mol. wt. 243.3 M.f. C 6 H 14 NO 3 PS 2 COMMERCIALISATION: History Insecticide and acaricide reported by G. Lemetre et al. (Not. Mal. Piante, 1963, No. 64). Introduced by Bombrini Parodi-Delfno (later Snia Viscosa). 240 The Pesticide Manual Sixteenth Edition © BCPC 2012 ethylene dichloride APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact and systemic insecticide and acaricide. PRODUCTS: Discontinued products ‘Fitios’* (Snia Viscosa). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R21/22 ethylene bis(trichloroacetate) Herbicide NOMENCLATURE: IUPAC name ethylene bis(trichloroacetate) Chemical Abstracts name 1,2-ethanediyl bis(trichloroacetate) Other names ethylene glycol bis(trichloroacetate) CAS RN [2514–53–6] EC no 219–732–9 Smiles code ClC(Cl)(Cl)C(=O)OCCOC(=O)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 352.8 M.f. C 6 H 4 Cl 6 O 4 COMMERCIALISATION: History Herbicide introduced by Hooker Chemical Corp. (and later by Nor-Am). APPLICATIONS: Mode of action Total herbicide. PRODUCTS: Discontinued products ‘Glytac’* (Hooker). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xi; R38 ethylene dichloride Insecticide IRAC 8A NOMENCLATURE: Common name dichlorure d’é(thylè) (F-ISO, accepted in lieu of a common name); EDC (JMAF); ethylene dichloride (BSI, E-ISO, ESA, accepted in lieu of a common name) IUPAC name 1,2-dichloroethane (I) ClCH 2 CH 2 Cl Supplementary Entries – Extended N-ethylmercurio-4-toluenesulfonanilide 241 Chemical Abstracts name (I) CAS RN [107–06–2] EC no 203–458–1 Smiles code ClCCCl PHYSICAL CHEMISTRY: Mol. wt. 99.0 M.f. C 2 H 4 Cl 2 Form Colourless liquid, with a chloroform-like odour. M.p. -36 °C B.p. 83.5 °C V.p. 10.4 kPa (20 °C) Henry 2.39 × 10 2 Pa m 3 mol –1 (calc.) S.g./density 1.2569 (20 °C) Solubility In water 4.3 g/l (room temperature). Soluble in most organic solvents. F.p. 12–15 °C (Abel Pensky); lower and upper limits of fammability in air 275 and 700 mg/l COMMERCIALISATION: History Reported as a component of insecticidal fumigants by R. T. Cotton & R. C. Roark (J. Econ. Entomol., 1927, 20, 636). APPLICATIONS: Mode of action Fumigant insecticide. Uses An insecticidal fumigant used mainly in stored products. PRODUCTS: Discontinued products ‘EDC’* (Toyo). ANALYSIS: Product analysis by glc (AOAC Methods, 18th Ed., 966.05). Residues in stored cereals determined by glc with ECD (ibid., 977.18; K. A. Scudamore, Anal. Methods Pestic. Plant Growth Regul., 1988, 16, 207, 231; Analyst (London), 1974, 99, 570; Anal. Methods Residues Pestic., 1988, Part I). Methods reviewed by J. L. Daft in Comp. Anal. Profles,Chapter 11. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 176 (1995). JMPR Evaln. 33 (1979). CAG. HSG 55 (1991). ICSC.250 (1995). IARC 20 (1979); 71 (1999). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEC as amended by 87/181/EEC. MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 670–890, mice 870–950, rabbits 860–970 mg/kg. ADI/RfD (JMPR) No ADI [1994]. Water GV 0.03 mg/l (see note on carcinogens). Toxicity Class WHO (a.i.) FM EC Classifcation F; R11| Xn; R22| Xi; R36/37| N; R52, R53| concn. dep. PIC Yes. N-ethylmercurio-4-toluenesulfonanilide Fungicide NOMENCLATURE: IUPAC name N-ethylmercurio-4-toluenesulfonanilide; N-(ethylmercury)-p- toluenesulfonanilide Chemical Abstracts name ethyl(4-methyl-N-phenylbenzenesulfonamidato-N)mercury CAS RN [517–16–8] Smiles code CC[Hg]N(c1ccccc1)S(=O)(=O)c2ccc(C)cc2 242 The Pesticide Manual Sixteenth Edition © BCPC 2012 N-(2-ethyl-2H-pyrazol-3-yl)-N′-phenylurea PHYSICAL CHEMISTRY: Mol. wt. 476.0 M.f. C 15 H 17 HgNO 2 S COMMERCIALISATION: History Fungicide introduced by E. I. du Pont de Nemours & Co. PRODUCTS: Discontinued products ‘Ceresan M’* (DuPont); ‘Granosan M’* (DuPont). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 9 (1967) EU Status (1107/2009) Alkyl mercury compounds considered to be outside the scope of the Directive; already banned, 79/117/EEC. MAMMALIAN TOXICOLOGY: EC Classifcation Not specifed, but organic mercury generally is assigned T+; R26/27/28| R33| N; R50, R53, concentration-dependent. PIC Not specifcally listed in the relevant DGD, but all mercury compounds are included in the PIC procedure. N-(2-ethyl-2H-pyrazol-3-yl)-N′-phenylurea Plant growth regulator NOMENCLATURE: IUPAC name N-(2-ethyl-2H-pyrazol-3-yl)-N′-phenylurea Chemical Abstracts name N-(1-ethyl-1H-pyrazol-5-yl)-N′-phenylurea Other names azoluron CAS RN [4058–90–6] Smiles code CCn1nccc1NC(=O)Nc2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 230.3 M.f. C 12 H 14 N 4 O Form Colourless crystals. M.p. 201–202 °C S.g./density 1.18 (25 °C) Solubility In water 365 mg/l (25 °C). In acetone 20.3, chloroform 2.3 (both in g/l, 25 °C). Soluble in ethanol; sparingly soluble in diethyl ether; almost insoluble in benzene and hexane. Stability Stable under normal conditions. Hydrolysed rapidly in strong acids and alkalis; DT 50 (pH 7) 180 d. COMMERCIALISATION: History Plant growth regulator introduced by Fahlberg-List to stimulate fower formation in glasshouse tomatoes. APPLICATIONS: Biochemistry Plant growth regulator with cytokinin-like activity, stimulating cell division, organ formation and cell elongation (i.e. internodes), as well as seed germination. Uses In combination with gibberellic acid, used to stimulate fower formation in glasshouse tomatoes, and thus to produce a higher yield of early tomatoes. N N NHCONH CH 2 CH 3 Supplementary Entries – Extended etnipromid 243 ANALYSIS: Product by potentiometric titration with perchloric acid in acetic acid. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2700 mg/kg. NOEL (90 d) for rats 25 mg/kg daily. ENVIRONMENTAL FATE: Plants Degradation in plants probably involves splitting of the urea bond, with hydroxylation and glycosidation of the aromatic metabolites. etinofen Herbicide NOMENCLATURE: Common name é(tinofè) ((m) F-ISO); etinofen (BSI, E-ISO) IUPAC name α-ethoxy-4,6-dinitro-o-cresol Chemical Abstracts name 2-(ethoxymethyl)-4,6-dinitrophenol CAS RN [2544–94–7] Smiles code CCOCc1cc(cc([N+](=O)[O-])c1O)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 242.2 M.f. C 9 H 10 N 2 O 6 COMMERCIALISATION: History Herbicide introduced by C. H. Boehringer Sohn (later Shell Agrar). PRODUCTS: Discontinued products ‘Dinethon’* (Shell Agrar). etnipromid Herbicide NOMENCLATURE: Common name etnipromide ((m) F-ISO); etnipromid (BSI, E-ISO) IUPAC name (RS)-2-[5-(2,4-dichlorophenoxy)-2-nitrophenoxy]-N-ethylpropionamide Chemical Abstracts name (±)-2-[5-(2,4-dichlorophenoxy)-2-nitrophenoxy]- N-ethylpropanamide CAS RN [76120–02–0] unstated stereochemistry Development codes Hoe 39 106 Smiles code CCNC(=O)C(C)Oc1cc(Oc2ccc(Cl) cc2Cl)ccc1[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 399.2 M.f. C 17 H 16 Cl 2 N 2 O 5 COMMERCIALISATION: History Herbicide evaluated by Hoechst AG. 244 The Pesticide Manual Sixteenth Edition © BCPC 2012 etrimfos etrimfos Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name etrimfos (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name O-6-ethoxy-2-ethylpyrimidin-4-yl O,O-dimethyl phosphorothioate Chemical Abstracts name O-(6-ethoxy-2-ethyl-4-pyrimidinyl) O,O- dimethyl phosphorothioate CAS RN [38260–54–7] EC no 253–855–9 Development codes SAN 197I Smiles code CCOc1cc(OP(=S)(OC)OC)nc(CC)n1 PHYSICAL CHEMISTRY: Mol. wt. 292.3 M.f. C 10 H 17 N 2 O 4 PS Form Colourless oil. M.p. -3.35 °C V.p. 6.5 mPa (20 °C); 18 mPa (30 °C); 49 mPa (40 °C) K ow logP >3.3 S.g./density 1.195 (20 °C) Solubility In water 40 mg/l (23–24 °C). Completely miscible with acetone, acetonitrile, chloroform, DMSO, ethanol, diethyl ether, ethyl acetate, hexane, kerosene, methanol, toluene, xylene. Stability Unstable when pure (c. 40% degradation in 28 d at 48–52 °C), but dilute solutions in non-polar solvents and its formulations are stable (c. 5% loss in 1 y at 18–22 °C). When stored in the dark at 22–24 °C for 28 d, no decomposition occurred in hexane, toluene, chloroform, acetone;c. 3% decomposition in methanol;c. 12% decomposition in ethyl acetate. Hydrolysis DT 50 (25 °C) 0.4 d (pH 3), 16 d (pH 6), 14 d (pH 9). High stability to light. COMMERCIALISATION: History Insecticide reported by H. J. Knutti & F. W. Reisser (Proc. Br. Insectic. Fungic. Conf., 5th, 1975, 2, 675). Introduced by Sandoz Agro AG (later Novartis Crop Protection AG). Manufacturers Novartis APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide and acaricide with contact and stomach action. Uses Control of Lepidoptera, Coleoptera, Diptera, and some Hemiptera at 250–750 g/ha on fruit trees (including citrus), vines, olives, potatoes, vegetables, maize, alfalfa, ornamentals, tobacco. Control of Pyralidae in paddy rice at 1.0–1.5 kg/ha. It was also used at 3–10 mg/kg for control of Lepidoptera, Coleoptera, mites, and lice in stored products. Phytotoxicity May be phytotoxic to begonias, and, for EC formulations, to cherries and some varieties of apple. Formulation types DP; EC; GR; LS; UL . Compatibility Not compatible with pesticides which are strongly alkaline. PRODUCTS: Discontinued products ‘Ekamet’* (Novartis); ‘Satisfar’* (Novartis). P(OCH 3 ) 2 S N N CH 3 CH 2 O CH 3 CH 2 O Supplementary Entries – Extended EXD 245 ANALYSIS: Product analysis by glc. Residues determined by glc (Man. Pestic. Residue Anal., pp. 6, 19; Anal. Methods Residues Pestic., 1988, Part I, M2, M5; J. C. Karpally et al., Anal. Methods Pestic. Plant Growth Regul., 1980, 11, 125; Analyst (London), 1985, 110, 765). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. JMPR Evaln. I 60 (1990); JMPR Evaln. 39 (1982). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1600–1800, mice 470–620 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000, male rabbits >500 mg/kg. Inhalation LC 50 (1 h) for rats >200 mg a.i. (as 50% EC)/l air. NOEL (90 d) for rats 9 mg/kg diet; (6 mo) for dogs 12 mg/kg diet; (2 y) for rats 6, dogs 10 mg/kg diet. ADI/RfD (JMPR) 0.003 mg/kg b.w. [1986]. Toxicity Class WHO (a.i.) II EPA (formulation) III EC Classifcation Xn; R22| N; R50, R53| concn. dep. ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for quail 740 mg/kg diet. Fish LC 50 (96 h) for carp and guppies 5.5 mg/l, rainbow trout 24 μ;g/l. Daphnia LC 50 (48 h) 0.0173 mg/l. Algae EC 50 (96 h) for Scenedesmus subspicatus 2.9 mg/l. Bees Toxic to bees by contact. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, etrimfos is rapidly metabolised and excreted, mainly in the urine. Metabolites include 6-ethoxy-4-hydroxy-2-ethylpyrimidine, 2-ethyl-4,6-dihydroxypyrimidine, 6-ethoxy-4-hydroxy-2-(1-hydroxyethyl)pyrimidine, and other isomers. Plants In plants, etrimfos undergoes rapid metabolism to 6-ethoxy-4- hydroxy-2-ethylpyrimidine, and small amounts of 2-ethyl-4,6-dihydroxypyrimidine and other hydroxylated derivatives. Soil/Environment Soil DT 50 3–10 d (o.c. 2.8%, pH 6.8). The principal degradation products are 6-ethoxy-4-hydroxy-2-ethylpyrimidine, small amounts of 2-ethyl-4,6-dihydroxypyrimidine and other hydroxylated derivatives, and CO 2 . EXD Herbicide NOMENCLATURE: Common name EXD (WSSA) IUPAC name O,O-diethyl dithiobis(thioformate) Chemical Abstracts name diethyl thioperoxydicarbonate; thioperoxydicarbonic acid ([(HO)C(S)]2S2) diethyl ester Other names dixanthogen CAS RN [502–55–6] EC no 207–944–4 Smiles code CCOC(=S)SSC(=S)OCC PHYSICAL CHEMISTRY: Mol. wt. 242.4 M.f. C 6 H 10 O 2 S 4 246 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenaminosulf COMMERCIALISATION: History Herbicide reported by E. K. Alban & L. McCombs (Proc. North Cent. Weed Control Conf., 1949, p. 81). Introduced by Roberts Chemicals Inc. and Monsanto Co. APPLICATIONS: Mode of action Contact herbicide. PRODUCTS: Discontinued products ‘Herbisan’* (Roberts Chemicals); ‘Sulfasan’* (Monsanto). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22 fenaminosulf Fungicide NOMENCLATURE: Common name fenaminosulf (BSI, E-ISO); phé(naminosulf) ((m) F-ISO); DAPA (JMAF) IUPAC name sodium 4-dimethylaminobenzenediazosulfonate Chemical Abstracts name sodium [4-(dimethylamino)phenyl]diazenesulfonate CAS RN [140–56–7] EC no 205–419–4 Development codes Bayer 22 555; Bayer 5072 Smiles code [Na+].CN(C)c1ccc(N=NS(=O)(=O)[O-])cc1 PHYSICAL CHEMISTRY: Mol. wt. 251.2 M.f. C 8 H 10 N 3 NaO 3 S Form Yellowish-brown powder. Solubility In water 40 g/kg (20 °C). Soluble in DMF; insoluble in benzene, diethyl ether, petroleum oils. Stability Stable ≤200 °C. Its aqueous solution is intense orange and is sensitive to light but is stabilised by sodium sulfte; stable in alkaline media. COMMERCIALISATION: History Fungicide reviewed by E. Urbschat (Angew. Chem., 1960, 72, 981). Introduced by Bayer AG. Patents DE 1028828 APPLICATIONS: Biochemistry Interferes with NADH-ubiquinone reductase (complex I). Uses Applied to seed or soil for the control of Pythium, Aphanomyces and Phytophthora spp. in soil at 45–110 g/100 kg seed (depending on the crop). Formulation types WP. PRODUCTS: Discontinued products ‘Dexon’* (Bayer); ‘Lesan’* (Bayer). ANALYSIS: Product analysis by polarography. Residues determined by colorimetry (D. MacDougall, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 3, 49). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. Supplementary Entries – Extended fenapanil 247 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 60, guinea pigs 150 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >100 mg/kg. Toxicity Class WHO (a.i.) II EC Classifcation T; R25| Xn; R21| N; R52, R53 fenaminstrobin Acaricide NOMENCLATURE: Common name fenaminstrobin (pa ISO) IUPAC name methyl (E)-2-{α-[2-(2,4-dichloroanilino)-6-(trifuoromethyl)pyrimidin-4- yloxy]-o-tolyl}-3-methoxyacrylate Chemical Abstracts name methyl (αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6- (trifuoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate CAS RN [1257598–43–8] Development codes SYP–1620 Smiles code CO\C=C(C(OC)=O)/C1=C(COC2=CC(C(F)(F)F)=NC(NC3=CC=C(Cl) C=C3Cl)=N 2 )C=CC=C1 PHYSICAL CHEMISTRY: Mol. wt. 528.3 M.f. C 23 H 18 Cl 2 F 3 N 3 O 4 fenapanil Fungicide NOMENCLATURE: Common name fé(napanil) ((m) F-ISO); fenapanil (BSI, ANSI, E-ISO) IUPAC name (±)-2-(imidazol-1-ylmethyl)-2-phenylhexanenitrile; (±)-α-butyl-α- phenylimidazole-1-propanenitrile Chemical Abstracts name α-butyl-α-phenyl-1H-imidazole-1- propanenitrile CAS RN [61019–78–1] Development codes RH-2161 Smiles code CCCCC(Cn1ccnc1)(C#N)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 253.3 M.f. C 16 H 19 N 3 COMMERCIALISATION: History Fungicide evaluated by Rohm & Haas Co. CO 2 Me O H 3 C O N N HN Cl Cl CF 3 248 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenazafor APPLICATIONS: Biochemistry Sterol demethylation inhibitor. PRODUCTS: Discontinued products ‘Sisthane’* (Rohm & Haas). fenasulam Herbicide NOMENCLATURE: Common name fenasulam (BSI, E-ISO) IUPAC name methyl 4-[2-(4-chloro-o-tolyloxy)acetamido]phenylsulfonylcarbamate; methyl (N-4-chloro-o-tolyloxyacetylsulfanilyl)carbamate Chemical Abstracts name methyl [[4-[[(4-chloro-2-methylphenoxy)acetyl]amino] phenyl]sulfonyl]carbamate CAS RN [78357–48–9] Development codes SSH-60 Smiles code COC(=O)NS(=O)(=O)c1ccc(NC(=O)COc2ccc(Cl)cc2C)cc1 PHYSICAL CHEMISTRY: Mol. wt. 412.9 M.f. C 17 H 17 ClN 2 O 6 S COMMERCIALISATION: History Herbicide evaluated by Shionogi and Co. Ltd. fenazafor Acaricide NOMENCLATURE: Common name fenazafor (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name phenyl 5,6-dichloro-2-trifuoromethylbenzimidazole-1-carboxylate Chemical Abstracts name phenyl 5,6-dichloro-2-(trifuoromethyl)-1H-benzimidazole-1- carboxylate CAS RN [14255–88–0] EC no 238–134–9 Development codes NC 5016 Smiles code FC(F)(F)c1nc2cc(Cl)c(Cl)cc2n1C(=O)Oc3ccccc3 PHYSICAL CHEMISTRY: Mol. wt. 375.1 M.f. C 15 H 7 Cl 2 F 3 N 2 O 2 COMMERCIALISATION: History Acaricide reported by D. T. Saggers & M. L. Clark (Nature (London), 1967, 215, 275). Introduced by Fisons Pest Control Ltd (later Schering Agriculture). APPLICATIONS: Mode of action Contact acaricide. PRODUCTS: Discontinued products ‘Lovozal’* (Schering); ‘Tarzol’* (Fisons). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. Supplementary Entries – Extended fenchlorazole-ethyl 249 MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R21/22| N; R50, R53 fenchlorazole-ethyl Herbicide safener NOMENCLATURE: Common name fenchlorazole (BSI, E-ISO, (m) F-ISO, for the carboxylic acid) IUPAC name ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3- carboxylate Chemical Abstracts name ethyl 1-(2,4-dichlorophenyl)-5-(trichloromethyl)- 1H-1,2,4-triazole-3-carboxylate CAS RN [103112–35–2]; [103112–36–3] acid EC no 401–290–5 Development codes Hoe 070542 (Hoechst); Hoe 072829 (acid) Smiles code acid:OC(=O)c1nc(n(n1)c2ccc(Cl)cc2Cl)C(Cl)(Cl)Cl;ester:CCOC(=O) c1nc(n(n1)c2ccc(Cl)cc2Cl)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 403.5; (acid 375.4) M.f. C 12 H 8 Cl 5 N 3 O 2 ; (acid C 10 H4Cl5N3O 2 ) Form White, practically odourless solid. M.p. 108–112 °C V.p. 8.9 × 10 –4 mPa (20 °C) (OECD 104) Henry 3.71 × 10 –4 Pa m 3 mol –1 (20 °C, calc.) S.g./density 1.7 (20 °C) Solubility In water 0.9 mg/l (pH 4.5, 20 °C). In n-hexane 2.5, methanol 27, toluene 270, acetone 360, dichloromethane >500 (all in g/l, 20 °C). Stability Aqueous hydrolysis DT 50 115 d (pH 5), 5.5 d (pH 7), 0.079 d (pH 9). COMMERCIALISATION: History Herbicide safener reported by H. Bieringer et al. (Proc. 1989 Br. Crop Prot. Conf. - Weeds, 1, 77). Fenchlorazole-ethyl introduced by Hoechst AG (later Bayer CropScience). Manufacturers Anhui Huaxing; Bayer CropScience APPLICATIONS: Biochemistry Fenchlorazole-ethyl synergises the activity of fenoxaprop-ethyl (or fenoxaprop-P-ethyl) in susceptible species by enhancing de-esterifcation to the acid, which is the active form. It also enhances the tolerance of wheat by accelerating the metabolic breakdown of fenoxaprop, leading to the formation of non-phytotoxic degradation products (J. C. Hall & G. R. Stephenson, Proc. Br. Crop Prot. Conf. – Weeds, 1995, 1, 261; J. C. Hall et al., Proc. 9th IUPAC Int. Congr. Pestic. Chem., London, 1998, 5E-005). Mode of action Applied to the foliage of wheat in combination with the grass herbicide fenoxaprop-ethyl or fenoxaprop-P-ethyl, it prevents growth retardation, leaf discoloration, Cl N N N CO 2 CH 2 CH 3 CCl 3 Cl 250 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenchlorphos and chlorosis of the crop. Uses Used as a safener for fenoxaprop-ethyl or fenoxaprop-P- ethyl in post-emergence control of grass weeds in wheat, durum wheat, rye, and triticale. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Considered to be outside the scope of the Directive; considered not to be a plant protection product. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000, mice >2000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and rabbits >2000 mg/kg. Non-irritating to eyes and skin (rabbits). Non-sensitising to skin (guinea pigs). Inhalation LC 50 (4 h) >1.52 mg/l. NOEL (90 d) for rats 1280, male mice 80, female mice 320, dogs 80 mg/kg diet; (1 y) for dogs 80 mg/kg diet. ADI/RfD (BfR) 0.0025 mg/kg b.w. [1991]. Toxicity Class WHO (a.i.) U EC Classifcation (R40) ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks >2400 mg/kg. Fish LC 50 (96 h) for rainbow trout 0.08 mg/l. Daphnia LC 50 (48 h) 1.8 mg/l. Bees Not harmful to bees; LC 50 (48 h) >300 μg/bee. fenchlorphos Insecticide IRAC 1B NOMENCLATURE: Common name fenchlorphos (BSI, E-ISO, (m) F-ISO, BAN); ronnel (ANSI, Canada, ESA, and formerly France) IUPAC name O,O-dimethyl O-2,4,5-trichlorophenyl phosphorothioate Chemical Abstracts name O,O-dimethyl O-(2,4,5-trichlorophenyl) phosphorothioate CAS RN [299–84–3] EC no 206–082–6 Development codes Dow ET-14; Dow ET-57 Smiles code COP(=S)(OC)Oc1cc(Cl)c(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 321.5 M.f. C 8 H 8 Cl 3 O 3 PS Form Colourless crystalline powder. M.p. Softens 35–37 °C; melts 40–42 °C V.p. 110 mPa (25 °C) Solubility In water 40 mg/l (room temperature). Readily soluble in most organic solvents including refned kerosine. Stability Stable ≤60 °C; stable in neutral and acidic media; hydrolysed by dilute alkali to the demethyl compound. COMMERCIALISATION: History Systemic insecticide introduced by Dow Chemical Co. Patents US 2599516, GB 699064. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide. Uses As a residual spray for the control of fies and other household pests. Also against ectoparasites of cattle, sheep and pigs; as a pour-on and backrubber application for lice and hornfy Supplementary Entries – Extended fenethacarb 251 control on cattle; as a dip against itch-mite (e.g. Psorergates ovis) and other ectoparasites of sheep. Also against cattle ectoparasites and in various preparations (oils and aerosol concentrates) as a wound dressing against blowly in livestock and for spot applications for the control of ticks on cattle. Formulation types AE; EC; PO; SA. Compatibility Incompatible with alkaline pesticides. PRODUCTS: Discontinued products ‘Korlan’* (Dow); ‘Nankor’* (Dow); ‘Trolene’* (Dow). ANALYSIS: Residues determined by glc, tlc or paper chromatography (AOAC Methods 18th Ed., 970.52). See also Pestic. Anal. Man., I, 303. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Evaln. 41 (1983). ICSC.975 (1995). EU Status (1107/2009) Never notifed to the EU. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1740 mg/kg. NOEL (2 y) for rats 1.5 mg/kg b.w. (EPA Tracking). ADI/RfD (JMPR) 0.01 mg/kg b.w. (1968); (EPA) 0.015 mg/kg b.w. [1987]. Toxicity Class WHO (a.i.) II EC Classifcation Xn; R21/22| N; R50, R53 fenethacarb Insecticide NOMENCLATURE: Common name fenethacarb (BSI, E-ISO); phé(né) ((m) F-ISO) IUPAC name 3,5-diethylphenyl methylcarbamate (I) Chemical Abstracts name (I) CAS RN [30087–47–9] Development codes BAS 235I (BASF) Smiles code CCc1cc(CC)cc(OC(=O)NC)c1 PHYSICAL CHEMISTRY: Mol. wt. 207.3 M.f. C 12 H 17 NO 2 COMMERCIALISATION: History Insecticide introduced by BASF AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. 252 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenfuthrin fenfuthrin Insecticide IRAC 3 NOMENCLATURE: Common name fenfuthrin (BSI, E-ISO); fenfuthrine ((f) F-ISO) IUPAC name 2,3,4,5,6-pentafuorobenzyl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethy lcyclopropanecarboxylate; 2,3,4,5,6-pentafuorobenzyl (1R,3S)-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate Chemical Abstracts name (1R-trans)-(pentafuorophenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate CAS RN [75867–00–4] Development codes NAK 1654 Smiles code CC1(C)C(C=C(Cl)Cl)C1C(=O) OCc2c(F)c(F)c(F)c(F)c2F PHYSICAL CHEMISTRY: Mol. wt. 389.2 M.f. C 15 H 11 Cl 2 F 5 O 2 Form Colourless crystals. M.p. 44.7 °C B.p. 130 °C /0.075 mmHg V.p. 1 mPa (20 °C) S.g./density 1.38 (20 °C) Specifc rotation [α]20 –16.8° (c = 1, chloroform) COMMERCIALISATION: History Insecticide reported by W. Behrenz & K. Naumann (Pfanz.-Nachr. Bayer (Engl. Ed.), 1982, 35, 309). Evaluated by Bayer AG. APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. Uses It shows a wide range of insecticidal activity against pests of stored products and in public hygiene. It has a good knock-down activity against Diptera, especially Culicidae. PRODUCTS: Discontinued products ‘Baynac’* (Bayer). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 90–105, female rats 85–120, male mice 119, female mice 150 mg/kg. Skin and eye Acute percutaneous LD 50 (24 h) for male ratsc. 2500, female rats 1535 mg/kg. Not a skin sensitiser (guinea-pigs). NOEL (90 d) for rats 200 mg/kg diet, for dogs 100 mg/kg diet Other Not mutagenic to mice. O O Cl Cl F F F F F 2,3,4,5,6-pentafluorobenzyl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate Supplementary Entries – Extended fenoprop; fenoprop-butotyl 253 fenitropan Fungicide NOMENCLATURE: Common name fenitropan (BSI, E-ISO); fé(nitropane) ((m) F-ISO) IUPAC name (1RS,2RS)-2-nitro-1-phenyltrimethylene di(acetate) Chemical Abstracts name (1R*,2R*)-2-nitro-1-phenyl-1,3-propanediyl diacetate CAS RN [65934–94–3] stated stereochemistry; [65934–95–4] unstated stereochemistry Development codes EGYT 2248 Smiles code CC(=O)OCC(C(OC(=O)C)c1ccccc1) [N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 281.3 M.f. C 13 H 15 NO 6 Form Colourless crystals. M.p. 70–72 °C Solubility In water 30 mg/l (20 °C). In chloroform 1.25, isopropanol 10, xylene 350 (all in g/l, 20 °C). COMMERCIALISATION: History Fungicide reported by A. Kis-Tamás et al. (Proc. Br. Crop Prot. Conf. - Pests Dis., 1981, 1, 29). Introduced by EGYT Pharmacochemical Works. Patents GB 1561422; US 4160035 APPLICATIONS: Mode of action Fungicide with contact action. Uses As a seed treatment for cereals, maize, rice and sugar beet; applied at 4–8 g/100 cwt seed, or 4–6 kg/ha as a foliar spray. Formulation types LS . PRODUCTS: Discontinued products ‘Volparox’* (EGYT). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 3237, female rats 3852 mg/kg. NOEL (90 d) for rats 2000 mg/kg diet. Toxicity Class WHO (a.i.) U fenoprop; fenoprop-butotyl Herbicide, plant growth regulator NOMENCLATURE: Common name 2,4,5-TP (France (as alternative to ISO name), JMAF and formerly USSR); silvex (ANSI, WSSA); fenoprop (BSI, E-ISO, (m) F-ISO) IUPAC name (±)-2-(2,4,5-trichlorophenoxy)propionic acid CH CH CH 2 NO 2 OCOCH 3 OCOCH 3 254 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenoprop; fenoprop-butotyl Chemical Abstracts name (±)-2-(2,4,5-trichlorophenoxy)propanoic acid CAS RN [93–72–1] fenoprop, unstated stereochemistry EC no 202–271–2 PHYSICAL CHEMISTRY: Mol. wt. 269.5; (butotyl ester 369.7) M.f. C 9 H 7 Cl 3 O 3 ; (butotyl ester C15H19Cl3O4) Form Colourless powder. M.p. 179–181 °C V.p. Its lower alkyl esters are slightly volatile; fenoprop-butometyl (2-butoxy-1-methylethyl ester) is practically non-volatile Solubility In water 140 mg/l (25 °C). In acetone 180, methanol 134, diethyl ether 98, heptane 0.86 (all in g/kg, 25 °C). The amine and alkali metal salts are soluble in water, acetone, lower alcohols; insoluble in aromatic and chlorinated hydrocarbons and most non-polar organic solvents. Its lower alkyl esters are sparingly soluble in water; very soluble in most organic solvents. pKa 2.84 COMMERCIALISATION: History The plant-growth regulating properties of its salts described by M. E. Synerholm & P. W. Zimmerman (Contrib. Boyce Thompson Inst., 1945, 14, 91). Its esters introduced as herbicides by Dow Chemical Co. (later DowElanco) and its salts as plant growth regulators by Amchem Products Inc. (later Rhône-Poulenc Agrochimie). APPLICATIONS: Mode of action Systemic, selective herbicide, absorbed by leaves and stems. Uses Recommended for brush control at 2–4 kg a.e./hl; to control aquatic weeds; to control broad-leaved weeds in maize and sugar cane at lower rates. Sprays of amine salts (1.4 a.e./hl) were used 7–14 d before harvest to reduce pre-harvest drop of apples. Formulation types EC (esters); SL (amine salts). PRODUCTS: Discontinued products ‘Fruitone T’* (Amchem); ‘Kuron’* (Dow). ANALYSIS: Product analysis by glc (CIPAC Handbook, 1994, F, 292–319; ibid., 1985, 1C, 2257); total acids by titration or by glc (ibid., 1985, 1C, 2121, 2122). Free phenol impurity determined by hplc (ibid., 1994, F, 362). Residues determined by glc with ECD (R. P. Marquardt, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 4, 211; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 688). See also Pestic. Anal. Man., I, 208, 302. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: IARC 41 (1986), Suppl. 7 (1987). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: IARC Class Chlorophenoxy herbicides classifed as 2B Oral Acute oral LD 50 for rats 650 mg/kg, 500–1000 mg mixed fenprop-butyl or propylene glycol butyl ether esters/kg,c. 3940 mg a.e. (as fenoprop-trolamine)/kg. Skin and eye Acute percutaneous LD 50 for rabbits >3200 mg a.e. (as fenoprop-trolamine)/ kg. Fenoprop, the trolamine salt and undiluted esters are eye irritants. Water GV 9 μg/l Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| Xi; R38| N; R50, R53 (acid): Xn; R20/21/22| Xi; R38| N; R50, R53 (salts) Supplementary Entries – Extended fenoxaprop-ethyl; fenoxaprop 255 fenoxacrim Insecticide NOMENCLATURE: Common name fé(noxacrim) ((m) F-ISO); fenoxacrim (BSI, E-ISO) IUPAC name 3′,4′-dichloro-1,2,3,4-tetrahydro-6-hydroxy-1,3-dimethyl-2,4- dioxopyrimidine-5-carboxanilide Chemical Abstracts name N-(3,4-dichlorophenyl)hexahydro-1,3-dimethyl-2,4,6-trioxo- 5-pyrimidinecarboxamide (preferred tautomer) Other names HHP CAS RN [65400–98–8] Smiles code CN1C(=O)C(C(=O)Nc2ccc(Cl)c(Cl)c2)C(=O)N(C)C1=O PHYSICAL CHEMISTRY: Mol. wt. 344.2 M.f. C 13 H 11 Cl 2 N 3 O 4 COMMERCIALISATION: History Insecticide discovered by Ciba-Geigy AG. fenoxaprop-ethyl; fenoxaprop Herbicide HRAC A WSSA 1 NOMENCLATURE: Common name (for acid) fé(noxaprop) ((m) F-ISO); (for acid) fenoxaprop (BSI, ANSI, E-ISO) IUPAC name ethyl (±)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionate; ethyl (±)-2-[4-(6-chlorobenzoxazol-2-yloxy)phenoxy]propionate Chemical Abstracts name ethyl (±)-2-[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy] propanoate CAS RN [82110–72–3] fenoxaprop-ethyl (racemate); [66441–23–4] fenoxaprop-ethyl (unstated stereochemistry); [95617–09–7] fenoxaprop (racemate); [73519–55–8] fenoxaprop (unstated stereochemistry) EC no 266–362–9 fenoxaprop-ethyl Development codes Hoe 033171; Hoe 053022 (acid) PHYSICAL CHEMISTRY: Mol. wt. 361.8; (acid 333.7) M.f. C 18 H 16 ClNO 5 ; (acid C16H 12 ClNO 5 ) Form Colourless solid. M.p. 85–87 °C V.p. 4.2 × 10 –3 mPa (20 °C) K ow logP = 4.12 S.g./density 1.3 Solubility In water 0.9 mg/l (pH 7, 25 °C). In acetone >500, toluene >300, ethyl acetate >200, ethanol, cyclohexane, n-octanol >10 (all in g/ kg, 25 °C). Stability Fenoxaprop-ethyl is stable for 6 months at 50 °C. Not sensitive to sunlight. Decomposed by aqueous acids and alkalis; DT 50 >1000 d (pH 5), 100 d (pH 7), 2.4 d (pH 9) (20 °C). Cl N O O O CHCO 2 C 2 H 5 CH 3 256 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenoxaprop-ethyl; fenoxaprop COMMERCIALISATION: History Herbicide reported by H. Bieringer et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1982, 1, 11). The ethyl ester introduced by Hoechst AG (later AgrEvo GmbH). Manufacturers AgrEvo APPLICATIONS: Biochemistry Fatty acid synthesis inhibitor, by inhibition of acetyl CoA carboxylase (ACCase). Mode of action Fenoxaprop-ethyl is a selective herbicide with contact and systemic action, absorbed principally by the leaves, with translocation both acropetally and basipetally to the roots or rhizomes. Uses Post-emergence control of many annual and perennial grass weeds (including Sorghum halepense) in soya beans, cotton, sugar beet, peanuts, potatoes, beans, sunfowers, vegetables, and other broad-leaved crops; and (when applied with the herbicide safener fenchlorazole-ethyl) annual and perennial grass weeds and wild oats in wheat, rye, and triticale. Formulation types EC. PRODUCTS: Discontinued products ‘Acclaim’* (Hoechst); ‘Bugle’* (Hoechst); ‘Cheetah’* (AgrEvo); ‘Cheetah R’* (AgrEvo); ‘Depon’* (AgrEvo); ‘Excel’* (AgrEvo); ‘Furore’* (AgrEvo); ‘Option’* (AgrEvo); ‘Option II’* (AgrEvo); ‘Puma’* (AgrEvo); ‘Whip’* (AgrEvo); ‘WhipI’* (AgrEvo); Discontinued mixtures ‘Cheyenne’* (+ MCPA-2-ethylhexyl) (Hoechst); ‘Fusion’* (+ fuazifop-P-butyl) (Zeneca); ‘Horizon’* (+ fuazifop-P-butyl) (AgrEvo). ANALYSIS: For analysis in residues, see Pestic. Anal. Man., II, 180.430. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: J. Pesticide Sci. 1992, 17, 17–23. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male mice 4670, female mice 5490, male rats 2357, female rats 2500 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >1000, female rats >2000 mg/kg. Slight irritant to skin and eyes (rabbits). Inhalation LC 50 (4 h) for rats >511 mg/m 3 . NOEL (3 y) for dogs 0.9 mg/kg b.w. (15 ppm). ADI/RfD (EPA) 0.0025 mg/kg b.w. [1986]. Toxicity Class WHO (a.i.) U EC Classifcation R43| N; R50, R53 (fenoxaprop-ethyl) ECOTOXICOLOGY: Birds Acute oral LD 50 for Japanese quail >5000, bobwhite quail >2510 mg/kg. Fish LC 50 (96 h) for river trout 0.48, bluegill sunfsh 0.31 mg/l. Daphnia LC 50 (48 h) 3.18 mg/l. Bees LD 50 >0.00002 mg/bee ENVIRONMENTAL FATE: Plants In plants, fenoxaprop-ethyl is metabolised via fenoxaprop to 6-chloro-2,3- dihydrobenzoxazol-2-one. Soil/Environment In soil, fenoxaprop-ethyl is rapidly hydrolysed to fenoxaprop (A. E. Smith J. Agric. Food Chem. 1985, 33, 483); DT 50 1–10 d. Supplementary Entries – Extended fenpiclonil 257 fenpiclonil Fungicide FRAC 12, E2; phenylpyrrole NOMENCLATURE: Common name fenpiclonil (BSI, E-ISO, (m) F-ISO) IUPAC name 4-(2,3-dichlorophenyl)pyrrole-3-carbonitrile Chemical Abstracts name 4-(2,3-dichlorophenyl)-1H-pyrrole-3-carbonitrile CAS RN [74738–17–3] Development codes CGA 142 705 (Ciba-Geigy) Smiles code Clc1cccc(c2c[nH]cc2C#N)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 237.1 M.f. C 11 H 6 Cl 2 N 2 Form White crystals. M.p. 144.9–151.1 °C V.p. 1.1 × 10-2 mPa (25 °C) K ow logP = 3.86 (25 °C) Henry 5.4 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.53 (20 °C) Solubility In water 4.8 mg/l (25 °C). In ethanol 73, acetone 360, toluene 7.2, n-hexane 0.026, n-octanol 41 (all in g/l, 25 °C). Stability Not hydrolysed after 6 h at 100 °C between pH 3 and 9. Stable up to 250 °C. COMMERCIALISATION: History Fungicide reported by D. Nevill et al. (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., 1, 65). Introduced in Switzerland (1988) by Ciba-Geigy AG (later Syngenta AG). Patents EP 236272 APPLICATIONS: Biochemistry Inhibits mitogen-activated protein kinase, in osmotic signal transduction. Mode of action Slightly systemic, contact fungicide with long-lasting activity. Uses Effective against seed-borne pathogens of cereals, especially Fusarium nivale and Tilletia caries. On non-cereal crops, controls a wide range of seed- and soil-borne fungi (Alternaria, Ascochyta, Aspergillus, Fusarium, Helminthosporium, Rhizoctonia and Penicillium spp.). Having a different mode of action, fenpiclonil gives good control of all isolates of F. nivale, including those resistant to carbendazim and related fungicides. On cereals and peas, used at 20 g/100 kg seed; on potatoes, at 20–50 g/t (depending on target pathogens). Formulation types DS; FS; WS . PRODUCTS: Discontinued products ‘Beret’* (Syngenta); ‘Electer’* (Novartis); ‘Galbas’* (Novartis); ‘Gambit’* (Novartis); Discontinued mixtures ‘Arena’* (+ tebuconazole) (seed treatment, Germany) (Bayer); ‘Larin’* (+ imazalil + tebuconazole) (seed treatment, Germany) (Syngenta). Cl Cl N CN H 258 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenpirithrin ANALYSIS: Residue determination by hplc. Details available from Syngenta. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats, mice, and rabbits >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Non-irritating to eyes and skin (rabbits). Non- sensitising (guinea pigs). Inhalation LC 50 (4 h) for rats >1.5 mg/l air. NOEL for rats 1.25, mice 20, dogs 100 mg/kg b.w. daily. ADI/RfD (BfR) 0.0125 mg/kg b.w. [1991]. Other Non- teratogenic and non-mutagenic. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail >2510 mg/kg. LC 50 for mallard ducks >5620, bobwhite quail 3976 ppm. Fish LC 50 (96 h) for rainbow trout 0.8, carp 1.2, bluegill sunfsh 0.76, catfsh 1.3 mg/l. Daphnia LC 50 (48 h) 1.3 mg/l. Algae LC 50 (5 d) for Scenedesmus subspicatus 0.22 mg/l. Bees Not toxic to honeybees; LD 50 (oral and contact) >5 μg/bee. Worms LC 50 (14 d) for Eisenia foetida 67 mg/kg soil. Other benefcial Harmless to carabid beetles. ENVIRONMENTAL FATE: Animals Rapidly absorbed from the gastrointestinal tract into the general circulation; rapidly excreted and almost completely eliminated, mostly in the faeces. The dominant metabolic pathway is oxidation of the pyrrole ring at the 2-position. A minor pathway is hydroxylation of the phenyl ring. All metabolites are excreted as conjugates, mainly as glucuronides. Plants Degradation proceeds via oxidation of the pyrrole ring followed by hydrolysis of the nitrile group. Opening of the pyrrole ring and hydroxylation of the phenyl ring are further degradation steps. The parent is, however, the relevant residue; between 13–15 minor metabolites were also observed. Soil/Environment Relatively persistent in soil; formation of bound residues represents the major route for dissipation. In leaching and adsorption/desorption experiments, the compound proved to be immobile in soil, RMF 0.3. Photolytic DT 50 in water 70 min. fenpirithrin Insecticide IRAC 3 NOMENCLATURE: Common name fenpirithrin (BSI, ANSI, E-ISO); fenpirithrine ((f) F-ISO) IUPAC name (RS)-cyano(6-phenoxy-2-pyridyl)methyl (1RS)-cis-trans-3-(2,2- dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate; (RS)-cyano(6-phenoxy-2-pyridyl) methyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate Chemical Abstracts name cyano(6-phenoxy-2-pyridinyl)methyl 3-(2,2-dichloroethenyl)- Supplementary Entries – Extended fenridazon 259 2,2-dimethylcyclopropanecarboxylate CAS RN [68523–18–2] unstated stereochemistry Development codes Dowco 417 Smiles code CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)c2cccc(Oc3ccccc3)n2 PHYSICAL CHEMISTRY: Mol. wt. 417.3 M.f. C 21 H 18 Cl 2 N 2 O 3 COMMERCIALISATION: History Insecticide evaluated by Dow Chemical Co. APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. PRODUCTS: Discontinued products ‘Vivithrin’* (Dow). fenridazon Plant growth regulator NOMENCLATURE: Common name fenridazon (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name 1-(4-chlorophenyl)-1,4-dihydro-6-methyl-4-oxopyridazine-3-carboxylic acid Chemical Abstracts name 1-(4-chlorophenyl)-1,4-dihydro-6-methyl-4-oxo-3- pyridazinecarboxylic acid CAS RN [68254–10–4]; [83588–43–6] potassium salt Development codes RH-0007 Smiles code Cc1cc(=O)c(nn1c2ccc(Cl)cc2)C(=O)O PHYSICAL CHEMISTRY: Mol. wt. 264.7 M.f. C 12 H 9 ClN 2 O 3 COMMERCIALISATION: History Plant growth regulator evaluated by Rohm & Haas Co. PRODUCTS: Discontinued products ‘Hybrex’* (potassium salt) (Monsanto). ANALYSIS: Residues by hplc/uv (Resid. Anal. Methods). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: NOEL (3 generation) for rats 100 ppm (5 mg/kg b.w.) (EPA Tracking). ADI/RfD (EPA) 0.05 mg/kg b.w. [1994]. N N C O OH O CH 3 Cl 260 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenson fenson Acaricide NOMENCLATURE: Common name fé(nizon) ((m) France); fenson (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name 4-chlorophenyl benzenesulfonate (I) Chemical Abstracts name (I) Other names CPBS; PCPBS CAS RN [80–38–6] Smiles code Clc1ccc(OS(=O)(=O)c2ccccc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 268.7 M.f. C 12 H 9 ClO 3 S Form Colourless crystals; (tech. is a pale pink powder). M.p. 61–62 °C; (tech., 56–59 °C) Solubility Sparingly soluble in water. Soluble in organic polar and aromatic solvents. Stability Hydrolysed by alkali. COMMERCIALISATION: History Introduced by Murphy Chemical Ltd (later DowElanco). APPLICATIONS: Mode of action Contact acaricide. Uses Acaricide with ovicidal properties which was normally used in combination with acaricides effective against the active stages of mites, to control mites on apples and glasshouse crops, including vines. Formulation types WP. PRODUCTS: Discontinued products ‘Murvesco’* (Murphy). ANALYSIS: Product analysis by hydrolysis to 4-chlorophenol which is determined by acid-base titration (CIPAC Handbook, 1970, 1, 392). Residues determined by colorimetry of a derivative (A. H. Kutschinski & E. N. Luce, Anal. Chem., 1952, 24, 1188). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1560–1740 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and rabbits >2000 mg/kg. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| Xi; R36| N; R51, R53 Supplementary Entries – Extended fensulfothion 261 fensulfothion Insecticide, nematicide IRAC 1B NOMENCLATURE: Common name fensulfothion (BSI, E-ISO, (m) F-ISO, ESA, Society of Nematologists USA) IUPAC name O,O-diethyl O-4-methylsulfnylphenyl phosphorothioate Chemical Abstracts name O,O-diethyl O-[4-(methylsulfnyl)phenyl] phosphorothioate Other names DMSP CAS RN [115–90–2] EC no 204–114–3 Development codes Bayer 25 141; S 767 Smiles code CCOP(=S)(OCC)Oc1ccc(cc1) S(=O)C PHYSICAL CHEMISTRY: Mol. wt. 308.4 M.f. C 11 H 17 O 4 PS 2 Form Yellowish-brown oil. M.p. <25 °C (Agchem. Desk Ref.) B.p. 138–141 °C /0.01 mmHg V.p. 4 mPa (US EPA, cited in ARS PPD) K ow logP = 2.23 (Agchem. Desk Ref.) S.g./density 1.202 (20 °C) Solubility In water 1.54 g/l (25 °C). Miscible with most organic solvents, except aliphatics. Stability Subject to hydrolysis in alkaline media. Readily oxidised to the sulfone, and isomerises readily to the O,S-diethyl isomer (E. Benjamini et al., J. Econ. Entomol., 1959, 52, 94, 99). COMMERCIALISATION: History Nematicide reported by B. Homeyer (Mitt. Biol. Bundesanst. Land-Forstwirtsch. Berlin- Dahlem, 1967, 121, 50). Introduced by Bayer AG. Patents DE 1101406; US 3042703 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Nematicide and insecticide with primarily contact action, but also some systemic activity. Uses Soil application for control of root-knot, cyst-forming, and free-living nematodes, and also soil-dwelling insects in cereals, maize, sorghum, cotton, rice, coffee, cocoa, peanuts, soya beans, sugar beet, sugar cane, tomatoes, potatoes, sweet potatoes, oranges, strawberries, bananas, pineapples, tobacco, ornamentals, and turf. Formulation types DP; GR; SL; SC. WP. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Dasanit’* (Bayer); ‘Terracur’* (Bayer); ‘Terracur P’* (Bayer). ANALYSIS: Product analysis by hplc with uv detection (AOAC Methods, 18th Ed., 983.09; CIPAC Handbook, 1985, 1C, 2126), by glc with uv detection (ibid., 1988, D, 92), or by glc with FID (AOAC Methods, 18th Ed., 986.07). Residues determined by glc (C. A. Anderson, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 253; Man. Pestic. Residue Anal., pp. 3, 6, 8, 13–17, P(OCH 2 CH 3 ) 2 S O CH 3 SO 262 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenteracol 19; Anal. Methods Residues Pestic., 1988, Part I, M2, M5). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) a general review of organophosphorus insecticides. JMPR Evaln. 39 (1982), 41 (1983). PDS 44 (1980). ICSC.406 (2001). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 4.7–10.5, female rats 2.2, guinea pigs 9 mg/kg. Skin and eye Acute percutaneous LD 50 (in xylene) for female rats 3.5, male rats 30 mg/kg. Inhalation LC 50 (1 h) for male rats 0.113 mg/l air. NOEL In 16 mo feeding trials, rats receiving 1 mg/kg diet showed no ill-effects. ADI/RfD (JMPR) 0.0003 mg/kg b.w. [1982]; (EPA) 0.00025 mg/kg b.w. [1989]. Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R27/28| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 40 mg/kg. Dietary LC 50 (5 d) for bobwhite quail 35, mallard ducks 43 mg/kg diet. Fish LC 50 (96 h) for bluegill sunfsh 0.12, rainbow trout 8.6, golden orfe 6.8 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Plants In plants, fensulfothion is readily oxidised. fenteracol Herbicide NOMENCLATURE: Common name fenteracol (BSI, E-ISO, (m) F-ISO) IUPAC name 2-(2,4,5-trichlorophenoxy)ethanol (I) Chemical Abstracts name (I) Other names TCPE CAS RN [2122–77–2] Smiles code OCCOc1cc(Cl)c(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 241.5 M.f. C 8 H 7 Cl 3 O 2 COMMERCIALISATION: History Herbicide introduced by Budapest Chemical Works. PRODUCTS: Discontinued products ‘Klorinol’* (Budapest Chemical). Supplementary Entries – Extended fenthiaprop; fenthiaprop-ethyl 263 fenthiaprop; fenthiaprop-ethyl Herbicide NOMENCLATURE: Common name fenthiaprop (BSI, E-ISO); fentiaprop ((m) F-ISO) IUPAC name (±)-2-[4-(6-chloro-1,3-benzothiazol-2-yloxy)phenoxy]propionic acid; (±)-2-[4-(6-chlorobenzothiazol-2-yloxy)phenoxy]propionic acid Chemical Abstracts name (±)-2-[4-[(6-chloro-2-benzothiazolyl)oxy]phenoxy]propanoic acid CAS RN [95721–12–3] fenthiaprop (racemate); [73519–50–3] fenthiaprop (unstated stereochemistry); [93921–16–5] fenthiaprop-ethyl (racemate); [66441–11–0] fenthiaprop- ethyl (unstated stereochemistry) Development codes Hoe 35 609 PHYSICAL CHEMISTRY: Mol. wt. 349.8; (ethyl ester 377.8) M.f. C 16 H 12 ClNO 4 S; (ethyl ester C18H16ClNO4S) Form Fenthiaprop-ethyl is a crystalline solid. M.p. 56–57.5 °C (ethyl ester) V.p. 5.10 × 10 –4 mPa (20 °C, ethyl ester) Solubility Ester: In water 0.8 mg/l (25 °C). In acetone, ethyl acetate, toluene >500 g/kg, cyclohexane >40 g/kg, ethanol, n-octanol >50 g/l. COMMERCIALISATION: History Herbicide reported by R. Handte et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1982, 1, 19). Ethyl ester, fenthiaprop-ethyl, introduced by Hoechst AG. APPLICATIONS: Mode of action Local and systemic herbicide; translocated acropetally and basipetally to roots and rhizomes, where the growing points are destroyed. Uses A post-em. herbicide, active against many annual and perennial grasses. It controls Alopecurus myosuroides, Avena spp. and volunteer cereals at 180–240 g/ha and Agropyron repens at 480–720 g/l in oilseed rape, potatoes and sugar beet. Formulation types EC. PRODUCTS: Discontinued products ‘Joker’* (ethyl ester) (Hoechst). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 977, female rats 917, male mice 1070, female mice 1170 mg/kg. Skin and eye Acute percutaneous LD 50 for female rats 2000 mg/kg. Slight irritant to skin and eyes (rabbits). NOEL (90 d) for rats 50 mg/kg diet. Toxicity Class WHO (a.i.) III 264 The Pesticide Manual Sixteenth Edition © BCPC 2012 fenuron fentrifanil Acaricide NOMENCLATURE: Common name fentrifanil (BSI, E-ISO, (m) F-ISO); hexafuoramin (Republic of South Africa) IUPAC name N-(6-chloro-α,α,α-trifuoro-m-tolyl)-α,α,α-trifuoro-4,6-dinitro-o-toluidine; 2′-chloro-2,4-dinitro-5′,6-bis(trifuoromethyl)diphenylamine Chemical Abstracts name N-[2-chloro-5-(trifuoromethyl)phenyl]-2,4-dinitro-6- (trifuoromethyl)benzenamine CAS RN [62441–54–7] Development codes PP199 Smiles code [O-][N+](=O)c1cc([N+](=O)[O-])c(Nc2cc(ccc2Cl)C(F)(F)F)c(c1)C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 429.7 M.f. C 14 H 6 ClF 6 N 3 O 4 COMMERCIALISATION: History Acaricide reported by N. Morton et al. (Proc. Br. Crop Prot. Conf. - Pests Dis., 1977, 2, 349). Evaluated by ICI Plant Protection Div. (later ICI Agrochemicals). APPLICATIONS: Uses Effective against Panonychus ulmi, Tetranychus spp. and eriophyid mites on apples. fenuron Herbicide HRAC C2 WSSA 7; urea NOMENCLATURE: Common name fenidim* (former exception, USSR); no name (Portugal, Sweden); fenuron (BSI, E-ISO, F-ISO, ANSI, WSSA) IUPAC name 1,1-dimethyl-3-phenylurea Chemical Abstracts name N,N-dimethyl-N′-phenylurea Other names PDU CAS RN [101–42–8] Smiles code CN(C)C(=O)Nc1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 164.2 M.f. C 9 H 12 N 2 O Form Colourless crystals. M.p. 133–134 °C V.p. 21 mPa (60 °C) S.g./density 1.08 (20 °C) Solubility In water 3.85 g/l (25 °C). In ethanol 108.8, diethyl ether 5.5, acetone 80.2, benzene 3.1, chloroform 125, hexane 0.2, groundnut oil 1.0 (all in g/kg, 20–25 °C). Stability Stable to light and to oxidation. Stable in neutral media, but hydrolysed by strong acids and alkalis. COMMERCIALISATION: History Herbicidal properties of fenuron described by H. C. Bucha & C. W. Todd (Science, 1951, 114, 493). Introduced by E. I. du Pont de Nemours & Co. Patents US 2655447, NHCON(CH 3 ) 2 Supplementary Entries – Extended fenuron-TCA 265 GB 691403, GB 692589 (all to DuPont) Manufacturers Hermania; ÉMV; United Phosphorus Ltd APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Non-selective systemic herbicide, absorbed predominantly by the roots, with translocation acropetally in the xylem. Uses Control of woody plants and deep-rooted perennial weeds, particularly on non-crop land. Often used in combination with chlorpropham to extend the weed spectrum and range of crops. Formulation types WP. PRODUCTS: Discontinued products ‘Dybar’* (DuPont); ‘Kayron’* (Krishi Rasayan); Discontinued mixtures ‘Atlas Gold’* (+ chlorpropham + propham) (Atlas); ‘Atlas Red’* (+ chlorpropham) (Nufarm UK); ‘Croptex Chrome’* (+ chlorpropham) (Hortichem). ANALYSIS: Product analysis of fenuron based on hydrolysis (W. K. Lowen & H. M. Baker, Anal. Chem., 1952, 24, 1476). Residues determined by colorimetry (R. L. Dalton & H. L. Pease, J. Assoc. Off. Agric. Chem., 1962, 45, 377). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 6400 mg/kg. Skin and eye Non-irritating to skin. NOEL In 90 d feeding trials, no apparent effect observed with rats receiving 500 mg/kg diet. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Fish LC 50 (48 h) for guppies 610 mg/l. ENVIRONMENTAL FATE: Plants In plants, N-demethylation occurs step-by-step. Soil/Environment In soil, enzymic and microbial degradation involves step-by-step N-demethylation. fenuron-TCA Herbicide NOMENCLATURE: Common name fenuron-TCA (WSSA) IUPAC name 1,1-dimethyl-3-phenyluronium trichloroacetate Chemical Abstracts name trichloroacetic acid compound with N,N-dimethyl- N-phenylurea (1:1) CAS RN [4482–55–7] Development codes GC-2603 Smiles code CN(C)C(=O)Nc1ccccc1.OC(=O)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 327.6 M.f. C 11 H 13 Cl 3 N 2 O 3 266 The Pesticide Manual Sixteenth Edition © BCPC 2012 famprop-methyl; famprop-isopropyl; famprop Form Colourless crystals. M.p. 65–68 °C Solubility In water 4.8 g/l (room temperature). In 1,2-dichloroethane 666, trichloroethylene 567 (both in g/kg, room temperature). Sparingly soluble in petroleum oils. COMMERCIALISATION: History Fenuron-TCA introduced by Allied Chemical Corp., Agricultural Division (later HACCO Inc.). Patents US 2782112, US 2801911 (both to Allied) APPLICATIONS: Uses Fenuron-TCA combines the herbicidal actions of fenuron and trichloroacetic acid, and was used for total weed control on non-crop areas and against woody plants. Formulation types WP. PRODUCTS: Discontinued products ‘Dozer’* (HACCO); ‘Urab’* (HACCO). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 4000–5700 mg/kg. Skin and eye Skin, eye, and respiratory tract irritant. Toxicity Class WHO (a.i.) U EC Classifcation Xi; R38| N; R50, R53 famprop-methyl; famprop-isopropyl; famprop Herbicide HRAC Z WSSA 25 NOMENCLATURE: Common name famprop (assigned to the acid) (BSI, E-ISO, (m) F-ISO, WSSA) IUPAC name methyl N-benzoyl-N-(3-chloro-4-fuorophenyl)-DL-alaninate; N-benzoyl-N- (3-chloro-4-fuorophenyl)-DL-alanine (acid) Chemical Abstracts name N-benzoyl-N-(3-chloro-4-fuorophenyl)-DL-alanine methyl ester CAS RN [52756–25–9] methyl ester; [52756–22–6] isopropyl ester; [58667–63–3] acid Development codes WL 29671 (methyl ester); WL 29 672 (isopropyl ester) (both Shell) Smiles code famprop:CC(N(C(=O)c1ccccc1)c2ccc(F)c(Cl)c2)C(=O)O PHYSICAL CHEMISTRY: Composition Tech is ≥93%. Mol. wt. methyl ester 335.8; isopropyl ester 363.8; acid 321.7 M.f. C 17 H 15 ClFNO 3 (methyl ester); C 19 H 19 ClFNO 3 (isopropyl ester); C16H13ClFNO3 (acid) Form Colourless crystals; (tech., off-white crystals). M.p. 84–86 °C; (tech., 81– 82 °C) V.p. Flamprop-methyl: 0.047 mPa (20 °C) K ow methyl ester, logP = 3.0; acid, logP = 3.09 (25 °C, unionised, K. Chamberlain et al., Pestic Sci. 47, 265 (1996)) C F Cl N CHCO 2 H CH 3 O Supplementary Entries – Extended famprop-methyl; famprop-isopropyl; famprop 267 Henry 4.51 × 10 –4 Pa m 3 mol –1 (famprop-methyl, calc.) Solubility Flamprop-methyl: in water 35 mg/l (20 °C). In acetone >500, cyclohexanone 414, o-xylene 258, carbon tetrachloride 168, ethanol 135, hexane 7 (all in g/l, 20 °C). Stability Stable to light and to heat, and at pH 2–7. Hydrolysed in alkaline media (pH >7) to famprop and methanol. pKa Acid, 3.7 (K. Chamberlain et al., Pestic. Sci., 1996, 47, 265 and refs. therein) COMMERCIALISATION: History Herbicidal properties of famprop-methyl reported by E. Haddock et al. (Proc. Br. Weed Control Conf., 12th, 1974, 1, 9); compared with analogues by B. Jeffcoat et al. (Pestic. Sci., 1977, 8, 1). Flamprop-isopropyl and famprop-methyl introduced by Shell Research Ltd (later American Cyanamid Co.); later replaced by the single stereoisomers (famprop-M- isopropyl and famprop-M-methyl). Patents GB 1437711 APPLICATIONS: Biochemistry Selectivity depends on the rates of hydrolysis to famprop and detoxication of the latter by formation of conjugates within the plant; the acid is translocated to meristems where it inhibits plant growth. Mode of action Flamprop-methyl is a selective systemic herbicide, absorbed by the leaves. Undergoes hydrolysis to famprop, which is translocated readily to growing points. Uses Post-emergence control of wild Oats (Avena spp.) in wheat, including crops undersown with clover or grass. Also controls Alopecurus myosuroides. Formulation types EC. Compatibility If applied together with phenoxy herbicides, the activity of famprop-methyl may be reduced. PRODUCTS: Discontinued products ‘Barnon’* (isopropyl ester) (Cyanamid). ANALYSIS: Product analysis by i.r. spectrometry or by glc. Residues determined by glc with ECD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1210, mice 720 mg/kg (famprop-methyl). Skin and eye Acute percutaneous LD 50 for rats >294 mg a.i./kg (as EC formulation). Non- irritating and non-sensitising to skin. NOEL (2 y) for rats 2.5 mg a.i./kg diet, for dogs 10 mg/kg diet. Other Acute i.p. LD 50 for rats 350–500 mg/kg. Toxicity Class WHO (a.i.) III (allocated to the acid) ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 4640, pheasants, mallard ducks, domestic fowl, partridges, pigeons >1000 mg/kg (famprop-methyl). Fish LC 50 (96 h) for rainbow trout 4.7 mg/l. Bees Non-toxic to bees. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, metabolism and elimination occur within 4 d. Plants In plants, famprop-methyl is hydrolysed to the biologically-active famprop, which then undergoes conversion to a biologically-inactive conjugate. 268 The Pesticide Manual Sixteenth Edition © BCPC 2012 fuacrypyrim fuacrypyrim Acaricide IRAC 20C NOMENCLATURE: Common name fuacrypyrime ((m) F-ISO); fuacrypyrim (BSI, E-ISO) IUPAC name methyl (E)-2-{α-[2-isopropoxy-6-(trifuoromethyl)pyrimidin-4-yloxy]-o- tolyl}-3-methoxyacrylate Chemical Abstracts name methyl (αE)-α-(methoxymethylene)-2-[[[2-(1-methylethoxy)- 6-(trifuoromethyl)-4-pyrimidinyl]oxy]methyl]benzeneacetate CAS RN [229977– 93–9]; [178813–81–5] unspecifed stereochemistry Development codes NA-83 Smiles code without stereochemistry:COC=C(C(=O)OC)c1ccccc1COc2cc(nc(OC(C) C)n2)C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 426.4 M.f. C 20 H 21 F 3 N 2 O 5 Form White, odourless solid. M.p. 107.2–108.6 °C V.p. 2.69 × 10 –3 mPa (20 °C) (gas saturation method) K ow logP = 4.51 (pH 6.8, 25 °C) Henry 3.33 × 10 –3 Pa m 3 mol –1 (20 °C, calc.) S.g./density 1.276 Solubility In water 3.44 × 10 –4 g/l (pH 6.8, 20 °C). In dichloromethane 579, acetone 278, xylene 119, acetonitrile 287, methanol 27.1, ethanol 15.1, ethyl acetate 232, n-hexane 1.84, n-heptane 1.60 (all in g/l, 20 °C). Stability Stable at pH 4 and 7; DT 50 574 d (pH 9). Aqueous photolysis DT 50 26 d. COMMERCIALISATION: History Acaricide registered in 2001 and launched in 2002, by Nippon Soda Co. Ltd. Manufacturers Nippon Soda APPLICATIONS: Biochemistry Mitochondrial complex III electron transport inhibitor (coupling site II). Mode of action Acaricide with contact and stomach action. Uses Control of Panonychus, at 10 g/100 l, for citrus; Panonychus and Tetranychus, at 15 g/100 l, for apples and pears. Formulation types SC. PRODUCTS: Discontinued products ‘Titaron’* (Nippon Soda); Discontinued mixtures ‘Oonata’* (+ chlorfenapyr) (Nippon Soda). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Never notifed to the EU. C CH O O O CH 3 CH 2 O N N CF 3 O CH CH 3 CH 3 CH 3 Supplementary Entries – Extended fuazolate 269 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male and female rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for male and female rats >2000 mg/kg. Weakly irritating for eyes; non- irritating for skin (rabbits). Inhalation LC 50 (4 h) for male and female rats >5.09 mg/l. NOEL (24 mo) for male rats 5.9 mg/kg b.w., for female rats 61.7 mg/kg b.w.; (18 mo) for male mice 20 mg/kg b.w.., for female mice 30 mg/kg b.w.; (12 mo) for male and female dogs 10 mg/kg b.w.. ADI/RfD (FSC) 0.059 mg/kg b.w. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail >2250 mg/kg. Dietary LC 50 for bobwhite quail >5620 ppm. Fish LC 50 (96 h) for carp 0.195 ppm. Daphnia LC 50 (48 h) 0.094 ppm. Algae EbC50 (72 h) for Selenastrum capricornutum 0.0173 ppm; ErC50 (72 h) for Selenastrum capricornutum 0.14 ppm. Bees LC 50 (oral) >300 ppm; LD 50 (contact) >10 μg/bee. Worms LC 50 for earthworms 23 mg/kg soil. Other benefcial No effect on Agistemus exsertus at 400 ppm. fuazolate Herbicide HRAC E WSSA 14; phenylpyrazole herbicide NOMENCLATURE: Common name fuazolate (BSI, E-ISO, (m) F-ISO) IUPAC name isopropyl 5-(4-bromo-1-methyl-5-trifuoromethylpyrazol-3-yl)-2-chloro-4- fuorobenzoate Chemical Abstracts name 1-methylethyl 5-[4-bromo-1-methyl-5-(trifuoromethyl)- 1H-pyrazol-3-yl]-2-chloro-4-fuorobenzoate CAS RN [174514–07–9] Development codes MON 48500 (Monsanto); JV 485 Smiles code CC(C)OC(=O) c1cc(c2nn(C)c(c2Br)C(F)(F)F)c(F)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 443.6 M.f. C 15 H 12 BrClF 4 N 2 O 2 Form Fluffy, white, crystalline solid. M.p. 79.5–80.5 °C V.p. 9.43 × 10 –3 mPa (20 °C) K ow logP = 5.44 Henry 7.89 × 10-2 Pa m 3 mol –1 (calc.) Solubility In water 53 μ;g/l (20 °C). Stability Stable at pH 4 and pH 5; DT 50 4201 d (pH 7, calc.), 48.8 d (pH 9) (both 20 °C). COMMERCIALISATION: History Reported by S. D. Prosch et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1997, 1, 45). Discovered by Monsanto Co. and evaluated by Twinagro, a j.v. of Monsanto and Bayer AG. N N Cl F Br CF 3 CH 3 (CH 3 ) 2 CHO O 270 The Pesticide Manual Sixteenth Edition © BCPC 2012 fuazuron Patents US 5489571; US 5587485; WO 9206962 Manufacturers Twinagro APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. Mode of action Causes rapid necrosis shortly after emergence of plants. Uses Under development for use as a pre- emergence cereal herbicide, controlling grasses such as Alopecurus myosuroides, Lolium spp., Apera spica-venti, Poa annua and Phalaris spp., as well as broad-leaved weeds such as Galium aparine, at 125–175 g/ha. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, 2002/748/EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Slightly irritating to eyes; not irritating to skin (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 for rats >1.7 mg/l. Other Negative in Ames, HGPRT/CHO, micronucleus and in vitro cytogenetic tests. ECOTOXICOLOGY: Birds Oral LD 50 for bobwhite quail and mallard ducks >2130 mg/kg. Dietary LC 50 for bobwhite quail and mallard ducks >5330 mg/kg. Fish LC 50 (96 h) for rainbow trout and bluegill sunfsh >0.045 mg/l. Daphnia EC 50 (48 h) >0.039 mg/l. Worms LC 50 (14 d) for earthworms >1170 mg/kg dry soil. ENVIRONMENTAL FATE: Soil/Environment Laboratory DT 50 (3 feld and 1 standard soil) 16–71 d. Strongly bound to soil: Kd and K oc in clay loam (pH 5.1, o.c. 1.94%) 2.5 × 10 2 and 1.3 × 10 4 , respy., in loam (pH 4.7, o.c. 4.24%) 2.9 × 10 2 and 0.7 × 10 4 , in silt loam (pH 6.3, o.c. 0.08%) 1.4 × 10 2 and 1.7 × 10 4 , in loamy sand (pH 5.8, o.c. 1.30%) 2.0 × 10 2 and 1.6 × 10 4 . Concentrations of fuazolate in lysimeter leachates were <0.01 μg/l. fuazuron Ixodicide IRAC 15 NOMENCLATURE: Common name fuazuron (BSI, E-ISO, (m) F-ISO, INN) IUPAC name 1-[4-chloro-3-(3-chloro-5-trifuoromethyl-2-pyridyloxy)phenyl]-3-(2,6- difuorobenzoyl)urea Cl F F NHCONHCO O N Cl CF 3 Supplementary Entries – Extended fuazuron 271 Chemical Abstracts name N-[[[4-chloro-3-[[3-chloro-5-(trifuoromethyl)-2- pyridinyl]oxy]phenyl]amino]carbonyl]-2,6-difuorobenzamide CAS RN [86811–58–7] Development codes CGA 157 419 (Ciba-Geigy) Smiles code Fc1cccc(F)c1C(=O) NC(=O)Nc2ccc(Cl)c(Oc3ncc(cc3Cl)C(F)(F)F)c2 PHYSICAL CHEMISTRY: Mol. wt. 506.2 M.f. C 20 H 10 Cl 2 F 5 N 3 O 3 Form White to pink, odourless, fne crystalline powder. M.p. 219 °C (decomp.) V.p. 1.2 × 10-7 mPa (20 °C) K ow logP = 5.1 (rp-tlc method) Henry <3.04 × 10 –6 Pa m 3 mol –1 (calc.) S.g./density 1.59 (20 °C) Solubility In water <0.02 ppm (20 °C). In methanol 2.4, isopropanol 0.9 (both in g/l, 20 °C). Stability Stable up to 219 °C. Hydrolysis DT 50 (25 °C) 14 d (pH 3), 7 d (pH 5), 20 h (pH 7), 0.5 h (pH 9). COMMERCIALISATION: History Ixodicide. Manufacturers Syngenta; E-tong APPLICATIONS: Biochemistry Interaction with chitin formation. Mode of action Systemic acarine growth regulator with contact and stomach action. Uses Strategic control of the cattle tick Boophilus microplus (including all known resistant strains) on beef cattle. Formulation types PO. PRODUCTS: Discontinued products ‘Acatak’* (Syngenta). ANALYSIS: By hplc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JECFA 48 (1997). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg (OECD 401). Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg (OECD 402). Inhalation LC 50 (4 h) for rats >5994 mg/m 3 (OECD 403). NOEL (1 y) for dogs 7.5 mg/kg b.w. daily; (life-time) for rats 400, mice (males and females) 4.5 mg/kg b.w. daily. In 2-generation reproduction tests (rats), NOEL 100 ppm. No carcinogenic, mutagenic, teratogenic or reprotoxicity potential. ADI/RfD (JMPR) 0.04 mg/kg b.w. [1997] (JECFA evaluation). Toxicity Class WHO (a.i.) III (company classifcation) ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail and mallard ducks >2000 mg/kg. LC 50 (8 d) for bobwhite quail and mallard ducks >5200 ppm. Fish LC 50 for rainbow trout >15, carp >9.1 mg/l (OECD class "harmful"). Daphnia LC 50 0.0006 mg/l (OECD class "very toxic"). Algae NOEC for freshwater green Algae 27.9 mg/l (virtually non-toxic). Bees OECD class "not toxic". Worms LC 50 (14 d) for earthworms >1000 mg/kg (not toxic) (OECD 207). 272 The Pesticide Manual Sixteenth Edition © BCPC 2012 fubenzimine ENVIRONMENTAL FATE: Animals See P. S. Tantiyaswasdikul in "Residues of some veterinary drugs in animal and foods" FAO Food and Nutrition Papers 41/10 (1998). Plants Not relevant. Soil/Environment Not investigated; environmental contamination is unlikely because of pour-on application. fubenzimine Acaricide NOMENCLATURE: Common name fubenzimine (BSI, E-ISO, (f) F-ISO) IUPAC name (2Z,4E,5Z)-N 2 ,3-diphenyl-N4,N5-bis(trifuoromethyl)-1,3-thiazolidine-2,4,5- triylidenetriamine Chemical Abstracts name N-[3-phenyl-4,5-bis[(trifuoromethyl)imino]-2- thiazolidinylidene]benzenamine CAS RN [37893–02–0] unstated stereochemistry EC no 253–703–1 Development codes BAY SLJ 0312 Smiles code FC(F)(F) N=C1SC(=Nc2ccccc2)N(C1=NC(F)(F)F)c3ccccc3 PHYSICAL CHEMISTRY: Mol. wt. 416.4 M.f. C 17 H 10 F 6 N 4 S Form Orange-yellowish powder. M.p. 118.7 °C V.p. <1 mPa (20 °C) Henry <2.60 × 10 –1 Pa m 3 mol –1 (calc.) Solubility In water 1.6 mg/l (20 °C). In dichloromethane, toluene >200, hexane, isopropanol 5–10 (all in g/l, 20 °C). Stability DT 50 29.9 h (pH 4), 30 min (pH 7), 10 min (pH 9) (22 °C). COMMERCIALISATION: History Acaricide reported by G. Zoebelein et al. (Mitt. Biol. Bundesanst. Land- Forstwirtsch., Berlin-Dahlem, 1979, 191, 283; Pfanz.-Nachr. Bayer (Engl. Ed.), 1980, 33, 169). Introduced by Bayer AG. APPLICATIONS: Mode of action Contact acaricide; acting as a mite growth regulator. The developent of larvae hatching from treated eggs and treated larvae and nymphs is retarded, and they fail to emerge from the next quiescent stage. Treated adult mites have a shorted life and lay fewer eggs. Uses Applied early at 500 mg/l, against Panonychus ulmi and Tetranychus spp. on pome fruit, plums and damsons, also against P. citri, Phyllocoptruta oleivora and Tetranychus spp. on citrus. Also shows some fungicidal activity. Formulation types WP. PRODUCTS: Discontinued products ‘Cropotex’* (Bayer). ANALYSIS: Residues determined by glc with ECD (G. Dräger, ibid., 1981, 34, 180). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. Supplementary Entries – Extended fucofuron 273 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats >5000 mg (in acetone + oil)/kg, 2840 mg (in water + ‘Cremophor’ EL)/kg, for female rats 3700–5000 mg (in acetone + oil)/kg, 2685 mg (in water + ‘Cremophor’ EL)/kg; for male mice >2500 mg/kg; for female rabbitsc. 360 mg/ kg; for female dogs >500 mg/kg. Skin and eye Acute percutaneous LD 50 (24 h) for rats >5000 mg/kg. Not a skin irritant; causes moderate to severe conjunctival irritation to rabbits. Inhalation (4 h) for rats >0.357 mg a.i. (as 50% WP)/l air. NOEL (90 d) for male dogs 100 mg/kg diet, for rats 500 mg/kg diet Other Not mutagenic in dominant lethal assays in mice; not embryotoxic or teratogenic in rabbits. Toxicity Class WHO (a.i.) U EC Classifcation Xi; R36| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for hens >5000, Japanese quail 4500–5000, canaries >1000 mg/kg. fucofuron Insecticide NOMENCLATURE: Common name fucofuron (BSI, E-ISO, (m) F-ISO) IUPAC name 1,3-bis(4-chloro-α,α,α-trifuoro-m-tolyl)urea Chemical Abstracts name N,N′-bis[4-chloro-3-(trifuoromethyl)phenyl]urea CAS RN [370–50–3] Smiles code FC(F)(F)c1cc(NC(=O)Nc2ccc(Cl)c(c2)C(F)(F)F) ccc1Cl PHYSICAL CHEMISTRY: Mol. wt. 417.1 M.f. C 15 H 8 Cl 2 F 6 N 2 O COMMERCIALISATION: History Insecticide developed by Ciba-Geigy AG. APPLICATIONS: Uses Insecticide used to control Tineidae larvae, which attack cotton fabrics. PRODUCTS: Discontinued products ‘Mitin N’* (Ciba-Geigy). Cl CF 3 NHCONH CF 3 Cl 274 The Pesticide Manual Sixteenth Edition © BCPC 2012 fucycloxuron fucycloxuron Acaricide, insecticide IRAC 15; benzoylurea NOMENCLATURE: Common name fucycloxuron (BSI, E-ISO, (m) F-ISO) IUPAC name 1-[α-(4-chloro-α-cyclopropylbenzylideneamino-oxy)-p-tolyl]-3-(2,6- difuorobenzoyl)urea (ratio 50–80% (E)- and 50–20% (Z)- isomers) Chemical Abstracts name N-[[[4-[[[[(4-chlorophenyl)cyclopropylmethylene]amino] oxy]methyl]phenyl]amino]carbonyl]-2,6-difuorobenzamide CAS RN [94050–52–9] (E)- isomer; [94050–53–0] (Z)- isomer; [113036–88–7] unstated stereochemistry Development codes PH 70–23; DU 319722 (both Duphar); UBI-A1335 (Uniroyal) Offcial codes OMS 3041 Smiles code Fc1cccc(F)c1C(=O)NC(=O) Nc2ccc(CON=C(C3CC3)c4ccc(Cl)cc4)cc2 PHYSICAL CHEMISTRY: Composition Ratio 50–80% (E)- and 50–20% (Z)- isomers. Mol. wt. 483.9 M.f. C 25 H 20 ClF 2 N 3 O 3 Form Off-white to yellow crystals (tech.). M.p. 143.6 °C (decomp.) (for (E)-, (Z)- isomeric mixture) V.p. 5.4 × 10 –5 mPa (25 °C) (for (E)-, (Z)- isomeric mixture) K ow logP = 6.97 (E)- isomer; 6.90 (Z)- isomer Henry 2.6 × 10-2 Pa m 3 mol –1 (25 °C) Solubility In water <1 μ;g/l (20 °C). In cyclohexane 0.2, xylene 3.3, ethanol 3.8, N-methylpyrrolidone 940 (all in g/l, 20 °C) for (E)-, (Z)- isomeric mixture. Stability Thermally stable, <2% decomposition after 24 hours storage at 50 °C. No degradation at pH 5, 7 or 9. Photolytically degraded, DT 50 c. 18 d. COMMERCIALISATION: History Acaricide and insecticide reported by A. C. Grosscurt et al. (Pestic. Sci., 1988, 22, 51). Introduced by Duphar B.V. (later Chemtura Corp.) in 1988. Patents EP 117320; US 4550202; US 4609676 Manufacturers Chemtura APPLICATIONS: Biochemistry Chitin synthesis inhibitor, type 0 (Lepidopteran). Mode of action Non- systemic acaricide and insecticide which inhibits the moulting process in mites and insects. It is only active against eggs and larval stages. Adult mites and insects are not affected. Uses Control of eggs and larval stages of eriophyid and tetranychid mite species on a variety of crops, including fruit crops, vegetables and ornamentals. Also controls larvae CH 2 F F NHCONHCO O N C Cl Supplementary Entries – Extended fucycloxuron 275 of a number of insects. Because of its relative selectivity, fucycloxuron is well-suited for integrated control programmes. Recommended concentration for control of mites on fruit crops is 0.01–0.015% a.i. On insects, good activity has been found against codling moth, leaf miners and some leaf rollers in pome fruit, at the same concentration. In ornamentals grown under glass/plastic, lower concentrations can be used. In grapes, the recommended dosage is 125–150 g/ha. Formulation types DC. PRODUCTS: Discontinued products ‘Andalin’* (Uniroyal). ANALYSIS: Product and residue analysis by hplc; details available from Chemtura. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Non-irritating to skin; mild eye irritant (rabbits). Inhalation LC 50 (4 h) for rats >3.3 mg/l air. NOEL In 2 y feeding trials, NOAEL for rats 120 mg/kg diet. In a 2-generation reproduction study, NOAEL for rats 200 mg/kg diet. Non-mutagenic and non- teratogenic. No evidence of carcinogenicity. Other Acute i.p. LD 50 for rats 2000 mg/kg. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks >2000 mg/kg. Dietary LC 50 (8 d) for mallard ducks and bobwhite quail >6000 mg/kg diet. Fish LC 50 (96 h) for rainbow trout and bluegill sunfsh >100 mg/l. Daphnia LC 50 (48 h) 0.27 μg/l. Algae NOEC for Selenastrum capricornutum >2.2 μ;g/l. Other aquatic spp. LC 50 (96 h) for mysid shrimps (Mysidopsis bahia) 340 ng/l. Bees Low toxicity to bees. Contact LD 50 for honeybees >100 μg/bee. Worms EC 50 (14 d) for earthworms >1000 mg/kg soil. Other benefcial Slightly to moderately harmful to predatory mites (IOBC). ENVIRONMENTAL FATE: Animals Poorly absorbed from gastrointestinal tract; mainly excreted as unchanged parent compound in the faeces. Flucycloxuron absorbed is metabolised and further excreted in the urine, mainly as 2,6-difuorobenzoic acid and N-(4-carboxyphenyl)-N′-(2,6- difuorobenzoyl)urea. Plants Non-systemic. Not metabolised on plants. Soil/Environment Strongly and irreversibly bound by soil/humic acid complex and virtually immobile in soil. Soil DT 50 0.25–0.5 y. 276 The Pesticide Manual Sixteenth Edition © BCPC 2012 fufenican fuenetil Acaricide, insecticide NOMENCLATURE: Common name fuenetil (BSI, E-ISO, (m) F-ISO); fué(né) (France) IUPAC name 2-fuoroethyl biphenyl-4-ylacetate Chemical Abstracts name 2-fuoroethyl [1,1′-biphenyl]-4-acetate CAS RN [4301–50–2] Development codes M 2060 Smiles code FCCOC(=O)Cc1ccc(cc1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 258.3 M.f. C 16 H 15 FO 2 Form Colourless crystals. M.p. 60.5 °C B.p. 177–180 °C /1 mmHg S.g./density 1.139 (68 °C) Solubility In water 2.5 mg/l (25 °C). In acetone >850, acetonitrile 810, benzene 760, ethanol 630, hexane 10, methanol 80, olive oil <0.7 (all in g/l, 25 °C). Stability Stable at pH 4, but hydrolysed at pH 7 and rapidly at pH 9. COMMERCIALISATION: History Insecticide reported by P. de Pietri-Tonelli et al. (Proc. Br. Insectic. Fungic. Conf., 3rd, 1965, p. 478). Introduced by Montecatini Edison S.p.A. (later Agrimont S.p.A.). Patents IT 710046; US 3436418 APPLICATIONS: Mode of action A selective, non-systemic acaricide and insecticide. Uses Applied in oil at 400–600 mg/kg in late winter to control winter eggs of Panonychus ulmi, Bryobia praetiosa, Aphididae, Psyllidae, some Lepidoptera and the winter stages of scale insects. PRODUCTS: Discontinued mixtures ‘Lambrol’* (+ petroleum oils) (Montecatini). ANALYSIS: Product analysis by glc or by hydrolysis to the corresponding acetic acid which was measured. Residues determined by glc or by colorimetry. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 8.7, mice 57, monkeys 75 mg/kg. Skin and eye Acute percutaneous LD 50 (10 d) for rabbits 7.5 mg/kg. NOEL (90 d) for rats 0.3 mg/kg daily. Toxicity Class WHO (a.i.) O EC Classifcation T+; R27/28 fufenican Herbicide NOMENCLATURE: Common name fufé(nican) ((m) F-ISO); fufenican (BSI, E-ISO) IUPAC name 2-(α,α,α-trifuoro-m-tolyloxy)nicotinanilide Chemical Abstracts name N-phenyl-2-[3-(trifuoromethyl)phenoxy]-3- pyridinecarboximide CAS RN [78863–62–4] Smiles code FC(F)(F)c1cccc(Oc2ncccc2C(=O)Nc3ccccc3)c1 Supplementary Entries – Extended fufenprox 277 PHYSICAL CHEMISTRY: Mol. wt. 358.3 M.f. C 19 H 13 F 3 N 2 O 2 COMMERCIALISATION: History Herbicide evaluated by May & Baker Ltd (later Rhône-Poulenc Agrochimie). fufenoxystrobin Fungicide NOMENCLATURE: Common name fufenoxystrobin (pa ISO) IUPAC name methyl (2E)-2-{2-[(2-chloro-α,α,α-trifuoro-p-tolyloxy)methyl]phenyl}-3- methoxyacrylate Chemical Abstracts name methyl (αE)-2-[[2-chloro-4-(trifuoromethyl)phenoxy] methyl]-α-(methoxymethylene)benzeneacetate CAS RN [918162–02–4] Development codes SYP–3759 Smiles code CO\C=C(C(OC)=O)/C1=C(COC2=CC=C(C(F)(F)F)C=C2Cl)C=CC=C1 PHYSICAL CHEMISTRY: Mol. wt. 400.8 M.f. C 19 H 16 ClF 3 O4 fufenprox Insecticide IRAC 3 NOMENCLATURE: Common name fufenprox (BSI, E-ISO, (m) F-ISO) IUPAC name 3-(4-chlorophenoxy)benzyl (RS)-2-(4-ethoxyphenyl)-3,3,3-trifuoropropyl ether Chemical Abstracts name 1-(4-chlorophenoxy)-3-[[2-(4-ethoxyphenyl)- 3,3,3-trifuoropropoxy]methyl]benzene CAS RN [107713–58–6] CF 3 H O CH 3 O CH 3 O O Cl O CH 3 CH 2 O CF 3 O Cl 278 The Pesticide Manual Sixteenth Edition © BCPC 2012 fumezin Development codes ICIA5682 Smiles code CCOc1ccc(cc1)C(COCc2cccc(Oc3ccc(Cl)cc3)c2)C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 450.9 M.f. C 24 H 22 ClF 3 O 3 Form Odourless, transparent pale yellow-green liquid. B.p. 204 °C /0.2 mmHg V.p. 1.3 × 10 –4 mPa (20 °C) S.g./density 1.25 (25 °C) Solubility In water 2.5 μ;g/l (pH 7). Soluble (>500 g/l) in hexane, toluene, acetone, dichloromethane, ethyl acetate, n-octanol, acetonitrile and methanol. COMMERCIALISATION: History Insecticide reported by R. F. S. Gordon et al. (Proc. Br. Crop Prot. Conf. - Pests Dis., 1992, 1, 81). Manufacturers Zeneca APPLICATIONS: Mode of action Insecticide with fast action and residual effcacy. Uses Control of Homoptera, Heteroptera, Coleoptera and Lepidoptera on rice, including rice hoppers. Formulation types DL; GR; EW; EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Mild skin and eye irritant (rabbits). Skin sensitiser (guinea pigs). ECOTOXICOLOGY: Fish LC 50 (96 h) for carp >10 mg tech./l, for red killifsh and Asian pond loach >10 mg/l as 0.5% dust or granule. Daphnia LC 50 for D. pulex (48 h) 0.00035 mg/l. Bees LD 50 0.03 μg/bee; NOEL 0.002 μg/kg. Worms LD 50 for Eisenia foetida >1000 mg/kg. Other benefcial Low toxicity to predatory arthropods. fumezin Herbicide NOMENCLATURE: Common name fumezin (BSI, E-ISO); fumé(zine) ((f) F-ISO) IUPAC name 2-methyl-4-(α,α,α-trifuoro-m-tolyl)-1,2,4-oxadiazinane-3,5-dione Chemical Abstracts name 2-methyl-4-[3-(trifuoromethyl)phenyl]-2H-1,2,4-oxadiazine- 3,5(4H,6H)-dione CAS RN [25475–73–4] Development codes BAS 348H (BASF) Smiles code CN1OCC(=O)N(C1=O)c2cccc(c2)C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 274.2 M.f. C 11 H 9 F 3 N 2 O 3 COMMERCIALISATION: History Herbicide evaluated by BASF AG. Supplementary Entries – Extended fumipropyn 279 fumipropyn Herbicide NOMENCLATURE: Common name fumipropyne ((m) F-ISO); fumipropyn (BSI, E-ISO) IUPAC name (±)-N-[4-chloro-2-fuoro-5-(1-methylprop-2-ynyl)oxyphenyl]cyclohex-1- ene-1,2-dicarboximide Chemical Abstracts name (±)-2-[4-chloro-2-fuoro-5-[(1-methyl-2-propynyl) oxy]phenyl]-4,5,6,7-tetrahydro-1H-isoindole-1,3(2H)-dione CAS RN [84478–52–4] Development codes S-23121 (Sumitomo Chemical) Smiles code CC(Oc1cc(N 2 C(=O) C3=C(CCCC3)C2=O)c(F)cc1Cl)C#C PHYSICAL CHEMISTRY: Mol. wt. 347.8 M.f. C 18 H 15 ClFNO 3 Form White to light brown crystals. M.p. 115–116.5 °C V.p. 0.28 mPa (20 °C) S.g./density 1.39 Solubility In water <1 mg/l (23 °C). In acetone 50%, ethyl acetate 33–50%, xylene 20–30%, methanol 5–10%, hexane >1% (all 23 °C). COMMERCIALISATION: History Reported by T. Hamada et al. (Proc. Br. Crop Prot. Conf. – Weeds 1989, 1, 41). Herbicide introduced by Sumitomo Chemical Co. Ltd for control of broad-leaved weeds in cereals. APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. Mode of action Systemic herbicide rapidly absorbed into plant tissues. Rapid necrosis or desiccation of stems and leaves is induced in the presence of light and oxygen. Soil application induces shoot necrosis. Uses Control of broad-leaved weeds including Galium aparine, Veronica spp.,and Viola,in cereals. Formulation types SC. EC. ANALYSIS: Product by glc. Residues by hplc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Minimal eye irritation; not a skin irritant (rabbits). Other Non- mutagenic in the Ames test. ECOTOXICOLOGY: Fish LC 50 (48 h) for carp >1 mg/l. N O O F Cl O CH C CH CH 3 280 The Pesticide Manual Sixteenth Edition © BCPC 2012 fuoridamid fuorbenside Acaricide NOMENCLATURE: Common name fuorbenside (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name 4-chlorobenzyl 4-fuorophenyl sulfde Chemical Abstracts name 1-chloro-4-[[(4-fuorophenyl)thio]methyl] benzene CAS RN [405–30–1] Development codes HRS 924; RD 2454 Smiles code Fc1ccc(SCc2ccc(Cl)cc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 252.7 M.f. C 13 H 10 ClFS Form Colourless crystals. M.p. 36 °C V.p. 10 mPa (20 °C) Solubility Practically insoluble in water. Very soluble in acetone and aromatic hydrocarbons; soluble in saturated hydrocarbons. Stability Resistant to hydrolysis but readily oxidised to the corresponding sulfoxide and sulfone. COMMERCIALISATION: History Acaricide reported by N. G. Clark et al. (J. Sci. Food Agric., 1957, 8, 566). Introduced by The Boots Co., Ltd Agriculture (later Schering Agriculture). Patents GB 748604 APPLICATIONS: Mode of action Non-systemic acaricide. Uses Effective against adult mites, its high volatility made it suitable for use in aerosols and in smokes. Formulation types Aerosols; smokes. PRODUCTS: Discontinued products ‘Fluorparacide’* (Boots); ‘Fluorsulphacide’* (Boots). ANALYSIS: Residues determined by oxidation to the sulfone which is measured colorimetrically as a derivative. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for ratsc. 3000 mg/kg. NOEL In 2 y feeding trials, rats receiving 100 mg/kg diet suffered no ill effect, but in 21 d trials, those receiving 50 mg/kg daily suffered slight liver and kidney enlargement. fuoridamid Plant growth regulator NOMENCLATURE: Common name fuoridamide ((m) F-ISO); fuoridamid (BSI, E-ISO, ANSI) IUPAC name 3′-(1,1,1-trifuoromethanesulfonamido)acet-p-toluidide Chemical Abstracts name N-[4-methyl-3-[[(trifuoromethyl)sulfonyl]amino] phenyl]acetamide CAS RN [47000–92–0] Development codes MBR-6033 Smiles code CC(=O)Nc1ccc(C)c(NS(=O)(=O)C(F)(F)F)c1 Supplementary Entries – Extended fuorodifen 281 PHYSICAL CHEMISTRY: Mol. wt. 296.3 M.f. C 10 H 11 F 3 N 2 O 3 S COMMERCIALISATION: History Plant growth regulator introduced by 3M Co. PRODUCTS: Discontinued products ‘Sustar’* (3M). fuorodifen Herbicide NOMENCLATURE: Common name fuorodifen (BSI, E-ISO, ANSI, WSSA, JMAF); fuorodifè(ne) ((m) F-ISO) IUPAC name 4-nitrophenyl α,α,α-trifuoro-2-nitro-p-tolyl ether Chemical Abstracts name 2-nitro-1-(4-nitrophenoxy)-4-(trifuoromethyl)benzene CAS RN [15457–05–3] Development codes C 6989 (Ciba) Smiles code [O-][N+] (=O)c1ccc(Oc2ccc(cc2[N+](=O)[O-])C(F)(F)F)cc1 PHYSICAL CHEMISTRY: Mol. wt. 328.2 M.f. C 13 H 7 F 3 N 2 O 5 Form Yellowish crystals. M.p. 94.0–94.5 °C V.p. 0.0093 mPa (20 °C) Henry 1.53 × 10 –3 Pa m 3 mol –1 (calc.) S.g./density 1.59 (20 °C) Solubility In water 2 mg/l (20 °C). In acetone 750, dichloromethane 680, hexane 1.4, methanol 4.5, n-octanol 10, toluene 400 (all in g/l, 20 °C). Stability No signifcant hydrolysis occured during 28 d at pH 1–9 (70 °C). COMMERCIALISATION: History Herbicide reported by L. Ebner et al. (Proc. Br. Weed Control Conf., 9th, 1968, 2, 1026). Introduced by Ciba AG (later Ciba-Geigy AG). Patents BE 628133; GB 1033163 APPLICATIONS: Mode of action Contact herbicide. Uses A pre-em. and post-em. contact herbicide used at 3–4 kg/ha. It was recommended pre-em. for use on drilled rice, but not for surface seeded rice. Formulation types EC. PRODUCTS: Discontinued products ‘Preforan’* (Ciba-Geigy). ANALYSIS: Product analysis by glc. Residues determined by glc with ECD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 9000 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats >3000 mg/kg. Not irritant to skin; moderate irritant to eyes (rabbits). Inhalation (6 h) for rats >0.99 mg/l air. NOEL (90 d) for rats 1000 mg/kg diet (67 mg/kg daily), for dogs 316 mg/kg diet (10 mg/kg daily). Toxicity Class WHO (a.i.) U 282 The Pesticide Manual Sixteenth Edition © BCPC 2012 fuoronitrofen fuoromidine Herbicide NOMENCLATURE: Common name fuoromidine (BSI (from 1984), E-ISO); furomidine ((f) F-ISO, (before 1984) BSI) IUPAC name 6-chloro-2-trifuoromethyl-3H-imidazo[4,5-b]pyridine Chemical Abstracts name 6-chloro-2-(trifuoromethyl)-1H-imidazo[4,5-b]pyridine CAS RN [13577–71–4] Development codes NC 4780 Smiles code FC(F)(F)c1nc2ncc(Cl)cc2[nH]1 PHYSICAL CHEMISTRY: Mol. wt. 221.6 M.f. C 7 H 3 ClF 3 N 3 COMMERCIALISATION: History Herbicide evaluated by Fisons Ltd (later Schering Agriculture). fuoronitrofen Herbicide NOMENCLATURE: Common name fuoronitrofen (BSI, E-ISO); fuoronitrofè(ne) ((m) F-ISO) IUPAC name 2,4-dichloro-6-fuorophenyl 4-nitrophenyl ether Chemical Abstracts name 1,5-dichloro-3-fuoro-2-(4-nitrophenoxy)benzene CAS RN [13738–63–1] Development codes Mo 500 Smiles code [O-][N+](=O)c1ccc(Oc2c(F)cc(Cl)cc2Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 302.1 M.f. C 12 H 6 Cl 2 FNO 3 COMMERCIALISATION: History Herbicide developed by Mitsui Toatsu Chemicals, Inc. (later Mitsui Chemicals, Inc.). APPLICATIONS: Biochemistry Inhibits protoporphyrinogen oxidase. PRODUCTS: Discontinued products ‘Mo500’* (Mitsui Toatsu). Cl O NO 2 Cl F Supplementary Entries – Extended fuotrimazole 283 fuothiuron Herbicide NOMENCLATURE: Common name fuothiuron (BSI, E-ISO, (m) F-ISO) IUPAC name 3-(3-chloro-4-chlorodifuoromethylthiophenyl)-1,1-dimethylurea Chemical Abstracts name N′-[3-chloro-4-[(chlorodifuoromethyl)thio]phenyl]- N,N-dimethylurea CAS RN [33439–45–1] Development codes BAY KUE 2079A Smiles code CN(C)C(=O)Nc1ccc(SC(F)(F)Cl)c(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 315.2 M.f. C 10 H 10 Cl 2 F 2 N 2 OS Form Colourless crystals. M.p. 113–114 °C V.p. <17 mPa (20 °C) Henry <7.34 × 10 –5 Pa m 3 mol –1 (calc.) Solubility In water 73 g/l (20 °C). In cyclohexanone 377, dichloromethane 316 (both in g/l, 20 °C). COMMERCIALISATION: History Herbicide introduced by Bayer AG. Patents GB 1314864; US 3931312 APPLICATIONS: Uses It was used at 2.5 g/ha to control dicotyledonous weeds in paddy rice. Formulation types EC; GR . PRODUCTS: Discontinued products ‘Clearcide’* (Bayer). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 336–554, mice 668–770 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >500 mg/kg. NOEL (90 d) for rats 40 mg/kg diet, for mice 20 mg/kg diet. fuotrimazole Fungicide NOMENCLATURE: Common name fuotrimazole (BSI, E-ISO, (m) F-ISO) IUPAC name 1-(3-trifuoromethyltrityl)-1H-1,2,4-triazole Chemical Abstracts name 1-[diphenyl[3-(trifuoromethyl)phenyl]methyl]-1H- 1,2,4-triazole CAS RN [31251–03–3] Development codes BAY BUE 0620 Smiles code FC(F)(F)c1cccc(c1)C(c2ccccc2)(c3ccccc3)n4cncn4 PHYSICAL CHEMISTRY: Mol. wt. 379.4 M.f. C 22 H 16 F 3 N 3 Form Colourless crystalline solid. M.p. 132 °C Solubility In water 0.0015 mg/l (20 °C). In cyclohexanone 200, dichloromethane 400, isopropanol 50, toluene 100 (all in g/kg, 20 °C). Stability Stable in 0.1M sodium hydroxide, but undergoesc. 40% degradation in 0.2M sulfuric acid in 24 h. COMMERCIALISATION: History Fungicide reported by F. Grewe & K. H. Büchel (Mitt. Biol. Bundesanst. Land- 284 The Pesticide Manual Sixteenth Edition © BCPC 2012 fupropacil Forstwirtsch. Berlin-Dahlem, 1973, 151, 208). Introduced by Bayer AG. Patents DE 1795249; US 3682950 APPLICATIONS: Biochemistry Sterol demethylation inhibitor. Uses A fungicide with specifc action against powdery mildew on barley, cucumbers, grapes, melons and peaches. Formulation types EC; WP. PRODUCTS: Discontinued products ‘Persulon’* (Bayer). ANALYSIS: Product analysis by i.r. spectroscopy. Residues determined by glc with FID (W. Specht, Pfanz.-Nachr. Bayer (Engl. Ed.), 1977, 30, 55; W. Specht & M. Tillkes ibid., 1980, 33, 61). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg. NOEL (2 y) for rats 50 mg/kg diet; (90 d) for rats 800 mg/kg diet, for dogs >5000 mg/kg diet. Toxicity Class WHO (a.i.) U fupropacil Herbicide NOMENCLATURE: Common name fupropacil (BSI, E-ISO, (m) F-ISO) IUPAC name isopropyl 2-chloro-5-(1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4- trifuoromethylpyrimidin-1-yl)benzoate Chemical Abstracts name 1-methylethyl 2-chloro-5-[3,6-dihydro-3-methyl-2,6- dioxo-4-(trifuoromethyl)-1(2H)-pyrimidinyl]benzoate CAS RN [120890–70–2] Development codes UCC-C4243 (Uniroyal) PHYSICAL CHEMISTRY: Mol. wt. 390.7 M.f. C 16 H 14 ClF 3 N 2 O 4 COMMERCIALISATION: History Herbicide evaluated by Uniroyal Chemical Co., Inc. APPLICATIONS: Biochemistry Inhibitor of protoporphyrinogen oxidase. Uses Control of many broad- leaved, and some annual grass weeds. CO 2 CH(CH 3 ) 2 N N F 3 C O O CH 3 Cl Supplementary Entries – Extended fupropadine; fupropadine hydrochloride 285 ENVIRONMENTAL FATE: Soil/Environment Aerobic soil DT 50 79 d; the major metabolite was the corresponding acid; there was negligible mineralisation to CO 2 . fupropadine; fupropadine hydrochloride Rodenticide NOMENCLATURE: Common name fupropadine (BSI, E-ISO, (f) F-ISO) IUPAC name 4-tert-butyl-1-[3-(α,α,α,α′,α′,α′-hexafuoro-3,5-xylyl)prop-2-ynyl]piperidine Chemical Abstracts name 1-[3-[3,5-bis(trifuoromethyl)phenyl]-2- propynyl]-4-(1,1-dimethylethyl)piperidine CAS RN [81613–59–4] fupropadine Development codes M&B 36 892 PHYSICAL CHEMISTRY: Mol. wt. 391.4; (hydrochloride 427.9) M.f. C2 0 H 23 F 6 N; (hydrochloride C20H24ClF6N) Form The hydrochloride is a solid. M.p. 201–202 °C (hydrochloride) Solubility In diethyl ether >150 g/l (5 °C). COMMERCIALISATION: History Rodenticide reported by A. P. Buckle (J. Hyg., 1985, 95, 505) and by F. P. Rowe et al. (ibid., p. 513). Introduced by May & Baker Ltd (later Rhône-Poulenc Agriculture). Patents EP 41324 APPLICATIONS: Uses Control of brown rats (Rattus norvegicus, including those resistant to anticoagulant rodenticides) around grain stores. Also controls house mice (Mus musculus). See W. Parnell, BCPC Monograph, 1987, No. 37, p. 125. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice 68 mg/kg. CF 3 CF 3 C C CH 2 N C(CH 3 ) 3 286 The Pesticide Manual Sixteenth Edition © BCPC 2012 furazole furazole Herbicide safener NOMENCLATURE: Common name furazole (WSSA) IUPAC name benzyl 2-chloro-4-trifuoromethyl-1,3-thiazole-5-carboxylate Chemical Abstracts name phenylmethyl 2-chloro-4-(trifuoromethyl)- 5-thiazolecarboxylate CAS RN [72850–64–7] EC no 276–942–3 Development codes MON 4606 (Monsanto) Smiles code FC(F)(F)c1nc(Cl)sc1C(=O)OCc2ccccc2 PHYSICAL CHEMISTRY: Composition Tech. is 98% pure. Mol. wt. 321.7 M.f. C 12 H 7 ClF 3 NO 2 S Form Colourless crystals, with a slight sweet odour; (tech. is a yellow to tan solid). M.p. 51–53 °C V.p. 3.9 × 10-2 mPa (25 °C) Henry 2.51 × 10-2 Pa m 3 mol –1 (calc.) S.g./density 0.96 (tech.) Solubility In water 0.5 mg/l (25 °C). Soluble in most organic solvents, including alcohols, ketones, and xylene. Stability Stable below 93 °C. F.p. 392 °C (tech.) (Tag closed cup) COMMERCIALISATION: History Herbicide safener introduced by Monsanto Co. in 1994. Manufacturers Monsanto APPLICATIONS: Biochemistry Enhances cytochrome P450-mediated oxidative metabolism of the herbicide, and its subsequent conjugation (see J. Davies & J. C. Caseley, Pestic. Sci. 1999, 55(11) 1043–1058). Uses Used as a herbicide safener. When applied as a seed protectant to grain sorghum, acts as a safener against the phytotoxic effects of herbicides containing alachlor or metolachlor. Formulation types Seed treatment; WG . PRODUCTS: Discontinued products ‘Screen’* (Monsanto). ANALYSIS: Details from Monsanto. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Considered to be outside the scope of the Directive; considered not to be a plant protection product. N S Cl CF 3 C O O CH 2 Supplementary Entries – Extended fuvalinate 287 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >5010 mg/kg. Non-irritating to skin; slightly irritating to eyes (rabbits). Not a skin sensitiser (guinea pigs). Inhalation No signifcant adverse health effects reported through occupational exposure. NOEL (90 d) for dogs ≤300 mg/kg daily, for rats ≤5000 mg/kg diet. EC Classifcation N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail >2510 mg/kg. Dietary LC 50 (5 d) for mallard ducks and bobwhite quail >5620 ppm. Fish LC 50 (96 h) for common carp 1.7, rainbow trout 8.5, bluegill sunfsh 11 mg/l. Daphnia LC 50 (48 h) 6.3 mg/l. ENVIRONMENTAL FATE: Soil/Environment Rapidly degraded in soil, with the formation of water-soluble metabolites. Breakdown is primarily microbial, with chemical breakdown of lesser importance. fuvalinate Acaricide, insecticide IRAC 3 NOMENCLATURE: Common name fuvalinate (BSI, ANSI, E-ISO, (m) F-ISO) IUPAC name (RS)-α-cyano-3-phenoxybenzyl N-(2-chloro-α,α,α-trifuoro-p-tolyl)-DL- valinate Chemical Abstracts name cyano(3-phenoxyphenyl)methyl N-[2-chloro-4- (trifuoromethyl)phenyl]-DL-valinate CAS RN [69409–94–5] Smiles code CC(C)C(Nc1ccc(cc1Cl)C(F)(F)F)C(=O)OC(C#N)c2cccc(Oc3ccccc3)c2 PHYSICAL CHEMISTRY: Mol. wt. 502.9 M.f. C 26 H 22 ClF 3 N 2 O 3 Form Tech. is a viscous yellow oil. B.p. >450 °C (extrapolated) V.p. <0.013 mPa (25 °C) K ow logP >3.8 S.g./density 1.29 Solubility In water <0.005 mg/kg. Freely soluble in alcohols, aromatic hydrocarbons, dichloromethane, diethyl ether. Stability DT 50 30 d (pH 3 and pH 6), 1–2 h (pH 9) (25 °C); 35 d (pH 3), 8 d (pH 6), 1 d (pH 9) (42 °C). Stable in glass >1.5 y (42 °C). In sunlight thin flms on glass or silica gel suffered 50% loss inc. 2 d, an aqueous emulsion (1.6 g/l) in glass in 12 d. COMMERCIALISATION: History Insecticide reported by C. A. Henrick et al. (Pestic. Sci., 1980, 11, 224) and by R. J. Anderson (J. Agric. Food Chem., 1985, 33, 508). Fluvalinate introduced by Zoecon Corp. (later Sandoz AG) and replaced by tau-fuvalinate (the D-valinate) [NOTE many references in the literature have been made, in error, to fuvalinate rather than to tau-fuvalinate]. Patents US 4411912; US 4260633 288 The Pesticide Manual Sixteenth Edition © BCPC 2012 FMC 1137 APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. Mode of action Contact insecticide and acaricide. Uses A broad-range, foliar-applied insecticide and acaricide effective at 56–168 g/ha against Aphididae, Cicadellidae, Lepidoptera, Thysanoptera, Tetranychidae and Trialeurodes vaporariorum on ornamentals, vegetables, trees and vines. Formulation types EC. PRODUCTS: Other products ‘Mavric’ (Nippon Soda); Discontinued products ‘Kaiser’* (Rocca); ‘Mavrik’* (Zoecon). ANALYSIS: Product analysis of pyrethroids reviewed by E. Papadopoulou-Mourkidou in Comp. Anal. Profles. By hplc (W. L. Fitch et al., Anal. Methods Pestic. Plant Growth Regul., 1984, 13, 79). Residues determined by glc with ECD (idem, ibid.; AOAC Methods, 18th Ed., 998.01; Resid. Anal. Methods; Environ. Chem. Methods). See also Pestic. Anal. Man., II, 180.427, 186.3400. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 6300 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats and rabbits >20 000 mg/kg. Mild skin irritant; mild to moderate eye irritant. NOEL (2 y) for rats 1 mg/kg b.w. daily (EPA IRIS). ADI/RfD (BfR) 0.005 mg/kg b.w. [1990]; (EPA) cRfD 0.01 mg/kg b.w. [1991]. Toxicity Class WHO (a.i.) II ENVIRONMENTAL FATE: Soil/Environment In sandy loam under aerobic conditions DT 50 c. 6 d. FMC 1137 Acaricide, insecticide IRAC 1B NOMENCLATURE: IUPAC name bis(diethoxyphosphinothioyl) disulfde (i) + bis(diisopropoxyphosphinothio yl) disulfde (ii) 75:25 mixture Chemical Abstracts name bis(diethoxyphosphinothioyl) disulfde (i) + bis[di-(1- methylethoxy)phosphinothioyl] disulfde (ii) CAS RN [2901–90–8] (i); [3031–21–8] (ii) Development codes FMC 1137; NIA 1137 PHYSICAL CHEMISTRY: Mol. wt. 370.4 (i); 426.6 (ii) M.f. C 8 H 20 O 4 P 2 S 4 (i); C 12 H 28 O 4 P 2 S 4 (ii) COMMERCIALISATION: History Insecticide and acaricide introduced by FMC Corp. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Supplementary Entries – Extended FMC 21861 289 PRODUCTS: Discontinued products ‘Phostex’* (FMC). FMC 19873 Herbicide NOMENCLATURE: IUPAC name 6-tert-butyl-3-isopropyl[1,2]thiazolo[3,4-d]pyrimidin-4(5H)-one; 6-tert- butyl-4,5-dihydro-3-isopropylisothiazolo[3,4-d]pyrimidin-4-one Chemical Abstracts name 6-(1,1-dimethylethyl)-3-(1-methylethyl)isothiazolo[3,4-d] pyrimidin-4(5H)-one CAS RN [40915–86–4] Development codes FMC 19873 Smiles code CC(C)c1snc2nc([nH]c(=O)c12)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 251.4 M.f. C 12 H 17 N 3 OS COMMERCIALISATION: History Herbicide evaluated by FMC Corp. FMC 21844 Herbicide NOMENCLATURE: IUPAC name 6-tert-butyl-3-isopropyl-1,2-oxazolo[5,4-d]pyrimidin-4(5H)-one; 6-tert- butyl-4,5-dihydro-3-isopropylisoxazolo[5,4-d]pyrimidin-4-one Chemical Abstracts name 6-(1,1-dimethylethyl)-3-(1-methylethyl)isoxazolo[5,4-d] pyrimidin-4(5H)-one CAS RN [35258–87–8] Development codes FMC 21844 Smiles code CC(C)c1noc2nc([nH]c(=O)c12)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 235.3 M.f. C 12 H 17 N 3 O 2 COMMERCIALISATION: History Herbicide evaluated by FMC Corp. FMC 21861 Herbicide NOMENCLATURE: IUPAC name 6-tert-butyl-3-propyl-1,2-oxazolo[5,4-d]pyrimidin-4(5H)-one; 6-tert-butyl- 4,5-dihydro-3-propylisoxazolo[5,4-d]pyrimidin-4-one Chemical Abstracts name 6-(1,1-dimethylethyl)-3-propylisoxazolo[5,4-d] pyrimidin-4(5H)-one CAS RN [35260–91–4] Development codes FMC 21861 290 The Pesticide Manual Sixteenth Edition © BCPC 2012 FMC 25213 Smiles code CCCc1noc2nc([nH]c(=O)c12)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 235.3 M.f. C 12 H 17 N 3 O 2 COMMERCIALISATION: History Herbicide evaluated by FMC Corp. FMC 23486 Herbicide NOMENCLATURE: IUPAC name 6-tert-butyl-3-isopropyl[1,2]oxazolo[3,4-d]pyrimidin-4(5H)-one; 6-tert- butyl-4,5-dihydro-3-isopropylisoxazolo[3,4-d]pyrimidin-4-one Chemical Abstracts name 6-(1,1-dimethylethyl)-3-(1-methylethyl)isoxazolo[3,4-d] pyrimidin-4(5H)-one CAS RN [38897–15–3] Development codes FMC 23486 Smiles code CC(C)c1onc2nc([nH]c(=O)c12)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 235.3 M.f. C 12 H 17 N 3 O 2 COMMERCIALISATION: History Herbicide reported by W. M. Dest et al. (Proc. Northeast. Weed Sci. Soc., 1973, 27, 31). Evaluated by FMC Corp. FMC 25213 Herbicide NOMENCLATURE: IUPAC name 2-ethyl-5-methyl-1,3-dioxan-5-yl 2-methylbenzyl ether; 2-ethyl-5-methyl-5- (2-methylbenzyloxy)-1,3-dioxane Chemical Abstracts name 2-ethyl-5-methyl-5-[(2-methylphenyl)methoxy]-1,3- dioxane CAS RN [41129–10–6] cis- isomer Development codes FMC 25213 Smiles code CCC1OCC(C)(CO1)OCc2ccccc2C PHYSICAL CHEMISTRY: Mol. wt. 250.3 M.f. C 15 H 22 O 3 COMMERCIALISATION: History Herbicide reported (Ann. Meet. South. Weed Sci. Soc., 27th, 1974) and evaluated by FMC Corp. Supplementary Entries – Extended fonofos 291 fonofos Insecticide IRAC 1B NOMENCLATURE: Common name fonofos (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name O-ethyl S-phenyl (RS)-ethylphosphonodithioate Chemical Abstracts name (±)-O-ethyl S-phenyl ethylphosphonodithioate CAS RN [944–22–9] unstated stereochemistry; [66767–39–3] racemate; [62705–71–9] (R)- isomer; [62680–03–9] (S)- isomer EC no 213–408–0 Development codes N-2790 (Stauffer) Smiles code CCOP(=S)(CC)Sc1ccccc1 PHYSICAL CHEMISTRY: Composition Tech. is 99.5%. The chiral forms have been isolated (R. Allahyari et al., J. Agric. Food Chem., 1977, 25, 471; P. W. Lee et al., Pestic. Biochem. Physiol., 1978, 8, 146, 158). Mol. wt. 246.3 M.f. C 10 H 15 OPS 2 Form Clear, colourless liquid, with an aromatic odour. B.p.c. 130 °C /0.1 mmHg V.p. 28 mPa (25 °C) K ow logP = 3.94 S.g./density 1.16 (25 °C) Solubility In water 13 mg/l (22 °C). Miscible with organic solvents, e.g. acetone, ethanol, methyl isobutyl ketone, xylene, kerosene. Stability Stable below 100 °C. Hydrolysed in acidic and alkaline media; DT 50 101 d (pH 4), 74–127 d (pH 7, depending on buffer), 1.8 d (pH 10) (40 °C). In light DT 50 12 d (pH 5, 25 °C). Specifc rotation Optical rotations of the chiral forms are reversed on solution in carbon tetrachloride, cyclohexane, methanol F.p. 179 °C COMMERCIALISATION: History Insecticide reported by J. J. Menn & K. Szabo (J. Econ. Entomol., 1965, 58, 734). Introduced by Stauffer Chemical Co. (later Zeneca Agrochemicals). APPLICATIONS: Biochemistry Cholinesterase inhibitor; proinsecticide, activated by metabolic oxidative desulfuration to the corresponding oxon. The (R)-isomer is more toxic to insects and mice and a more potent inhibitor of cholinesterase than the (S)-isomer. Mode of action Soil insecticide with contact and stomach action. Uses Control of soil insects (especially mole crickets, corn rootworms, symphylids, wireworms, Vine weevil larvae, cockchafer larvae, cabbage root fy, onion fy, carrot fy, wheat bulb fy, etc.) in cereals, maize, sorghum, vegetables, ornamentals, fruit (including citrus and bananas), vines, olives, potatoes, sugar beet, sugar cane, peanuts, tobacco, and turf at 1.0–1.5 kg/ha. Formulation types GR; MG; EC; SC. CS; Seed treatment. S P S CH 2 CH 3 OCH 2 CH 3 292 The Pesticide Manual Sixteenth Edition © BCPC 2012 fonofos PRODUCTS: Discontinued products ‘Capfos’* (Zeneca); ‘Cudgel’* (Zeneca); ‘Dyfonate’* (Zeneca); Discontinued mixtures ‘Edge’* (+ pebulate) (Zeneca); ‘Oslo’* (+ anthraquinone + oxine- copper) (Sopra). ANALYSIS: Product analysis by capillary glc (J. E. Barney et al., Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 269). Residues in crops, soil and water determined similarly (idem, ibid.; Environ. Chem. Methods). See also Pestic. Anal. Man., I, 204; ibid., II, 180.221. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. ICSC.708 (1997). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 11.5, female rats 5.5 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 147, rabbits 32–261, guinea pigs 278 mg/kg. Non-irritating to skin and eyes (rabbits). Weak skin sensitiser (guinea pigs). Inhalation LC 50 (4 h) for male rats 51, female rats 17 μg/l. NOEL (2 y) for rats 10 mg/kg diet (0.5 mg/kg b.w. daily); for dogs 0.2 mg/kg b.w. daily. Not carcinogenic or teratogenic. ADI/RfD (EPA) cRfD 0.002 mg/kg b.w. [1991]. Toxicity Class WHO (a.i.) Ia EPA (formulation) I or II EC Classifcation T+; R27/28| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks 128 mg/kg. Fish LC 50 (96 h) for rainbow trout 0.05, bluegill sunfsh 0.028 mg/l. Daphnia LC 50 (48 h) 1 μg/l. Bees Toxic to bees; LD 50 0.0087 mg/bee. ENVIRONMENTAL FATE: Animals Metabolism in animals is similar to that in plants. Plants In plants, metabolism involves oxidation to the phosphonothioate, and hydrolytic cleavage of the thiophenol residue. Soil/Environment Under aerobic conditions, fonofos at 10 ppm was degraded at a moderate rate, DT 50 3–16 weeks in soils ranging from loamy sand to clay loam to peat; adsorption K 15.3 (loam soil). The major degradate was O-ethyl ethanephosphonothioic acid; other degradates included fonofos oxon, O-ethyl ethanephosphonic acid, O-ethyl O-methylethyl phosphonate, diphenyl sulfde, methylphenyl sulfoxide and methylphenyl sulfone. Supplementary Entries – Extended formothion 293 formothion Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name formothion (BSI, E-ISO, (m) F-ISO, ESA, JMAF) IUPAC name S-[formyl(methyl)carbamoylmethyl] O,O-dimethyl phosphorodithioate; 2-dimethoxyphosphinothioylthio-N-formyl-N-methylacetamide Chemical Abstracts name S-[2-(formylmethylamino)-2-oxoethyl] O,O- dimethyl phosphorodithioate CAS RN [2540–82–1] EC no 219–818–6 Development codes J-38; SAN 6913I Smiles code COP(=S)(OC)SCC(=O)N(C)C=O PHYSICAL CHEMISTRY: Mol. wt. 257.3 M.f. C 6 H 12 NO 4 PS 2 Form Odourless, pale yellow, viscous liquid or crystalline mass. M.p. 25–26 °C B.p. Decomposes on distillation. V.p. 0.113 mPa (20 °C) S.g./density 1.361 (20 °C) Solubility In water 2.6 g/l (24 °C). Completely miscible with common organic solvents, e.g. alcohols, ethers, ketones, chloroform, benzene, toluene, xylene; slightly soluble in hexane; very slightly soluble in ligroin and paraffn oil. Stability EC hydrolysed by water to dimethoate and (dimethoxyphosphinothioylthio)acetic acid; DT 50 ≤1 d (pH 3–9, 23 °C). Hydrolysed more rapidly in alkaline media. Dilute solutions in non-polar organic solvents are stable. The a.i. is degraded inc. 28 d at 54 °C. COMMERCIALISATION: History Insecticide reported by C. Klotzsche (Mitt. Geb. Lebensmittelunters. Hyg., 1961, 52, 341). Introduced by Sandoz AG (later Novartis Crop Protection AG). Patents US 3176035; US 3178337 Manufacturers Novartis APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide with contact and stomach action. Uses Effective at 250–500 g/ha against a wide range of sucking and mining insects such as Aphididae, bugs, Cicadellidae, Coccidae, Diaspididae, Drosophilidae, Margarodidae, Psyllidae, Tephritidae and Thysanoptera, as well as against some chewing insects (Cydia pomonella and Epilachna spp.) and spider mites on a variety of feld crops, fruit trees, citrus and other tropical fruit, cotton, grapes, hops, ornamentals, rice, sugar cane, tobacco and vegetables. Phytotoxicity Phytotoxic to some varieties of peach, apricot and cherry. Formulation types EC; UL. Compatibility Incompatible with alkaline materials. S P(OCH 3 ) 2 S CH C NH O CH 3 CH O 294 The Pesticide Manual Sixteenth Edition © BCPC 2012 formparanate PRODUCTS: Discontinued products ‘Afix’* (Sandoz); ‘Anthio’* (Novartis); Discontinued mixtures ‘Anthiomix’* (+ fenitrothion) (Novartis). ANALYSIS: Product analysis by glc with FID (CIPAC Handbook, 1998, H, 178), or by glc with FPD (AOAC Methods, 18th Ed., 974.03). Residues determined by glc (A. Ambrus et al., J. Assoc. Off. Anal. Chem., 1981, 64, 733; M. Wisson et al., Anal. Methods Pestic. Plant Growth Regul., 1976, 8, 123). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Mtg. 83 (1998); JMPR Evaln. I 72 (1994), 84 (1998). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 365–500, mice 190–195, rabbits 570, cats 213 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats >1000 mg/kg. Slightly irritating to skin (rabbits). Inhalation LC 50 (4 h) for rats 3.2 mg/l air (as ‘Anthio’ 50ZP). NOEL In 2 y feeding trials, rats and dogs receiving 80 mg/kg diet showed no adverse effects. ADI/RfD (JMPR) ADI withdrawn [1996]. Water GV Excluded from GV derivation (U). Toxicity Class WHO (a.i.) II EPA (formulation) II EC Classifcation Xn; R21/22 ECOTOXICOLOGY: Birds Acute oral LD 50 for pigeons 630 mg/kg. Fish LC 50 (72 h) for carp 10 mg/l; (96 h) for rainbow trout 38.3 mg/l. Daphnia LC 50 (24 h) 16.1 mg/l. Algae EC 50 (96 h) for Scenedesmus subspicatus 42.3 mg/l. Bees Toxic to bees; LD 50 (oral) 1.537, (topical) 1.789, (contact, deposit) 28.447 μg/g b.w. Worms LC 50 (14 d) for earthworms 157.7 mg/kg soil. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, formothion is metabolised to (dimethoxyphosphinthioylthio)acetic acid and polar metabolites, and elimination occurs within 24 h. Plants In plants, formothion is metabolised to dimethoate (q.v.), (dimethoxyphosphinthioylthio)acetic acid, bis(dimethylthiophosphoryl) disulfde, omethoate (q.v.), and O,O-dimethyl hydrogen phosphorodithioate. Soil/Environment DT 50 in loamy soil <1 d, forming dimethoate (q.v.) and (dimethoxyphosphinthioylthio)acetic acid, which ultimately dissipate. formparanate Acaricide, insecticide NOMENCLATURE: Common name formparanate (BSI, E-ISO); formoparanate ((m) F-ISO) IUPAC name 4-dimethylaminomethyleneamino-m-tolyl methylcarbamate Supplementary Entries – Extended fosmethilan 295 Chemical Abstracts name N,N-dimethyl-N′-[2-methyl-4-[[(methylamino)carbonyl]oxy] phenyl]methanimidamide CAS RN [17702–57–7] Development codes UC 25 074 Smiles code CNC(=O)Oc1ccc(N=CN(C)C)c(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 235.3 M.f. C 12 H17N3O 2 COMMERCIALISATION: History Insecticide and acaricide evaluated by Union Carbide. APPLICATIONS: Biochemistry Cholinesterase inhibitor. fosmethilan Insecticide IRAC 1B NOMENCLATURE: Common name fosmé(thilane) ((m) F-ISO); fosmethilan (BSI, E-ISO) IUPAC name S-[N-(2-chlorophenyl)butyramidomethyl] O,O-dimethyl phosphorodithioate; 2′-chloro-N-(dimethoxyphosphinothioylthiomethyl)butyranilide Chemical Abstracts name S-[[(2-chlorophenyl)(1-oxobutyl)amino]methyl] O,O- dimethyl phosphorodithioate CAS RN [83733–82–8] Development codes NE-79 168 Smiles code CCCC(=O)N(CSP(=S)(OC)OC)c1ccccc1Cl PHYSICAL CHEMISTRY: Mol. wt. 367.8 M.f. C 13 H 19 ClNO 3 PS 2 Form Colourless crystals. M.p. 42 °C V.p. 12 mPa K ow logP = 0.56 Solubility In water 2.3 mg/l (20 °C). Stability On hydrolysis (20 °C) DT 50 12.7 d (pH 4.5), 13.1 d (pH 7), 11.4 d (pH 8.3). COMMERCIALISATION: History Insecticide reported by K. Sagi et al. (Proc. 10th Int. Congr. Plant Prot., 1983, 1, 384). APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses Control of Diptera, Hemiptera, Lepidoptera, Coleoptera, and Hymenoptera on pome fruit, stone fruit, vegetables, and feld crops. Formulation types EC. PRODUCTS: Discontinued products ‘Nevifos’* (Neviki); ‘Neviphos’* (Chemolimpex). P(OCH 3 ) 2 S CH 2 C O N Cl S CH 3 (CH 2 ) 2 296 The Pesticide Manual Sixteenth Edition © BCPC 2012 fosthietan TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 110 mg/kg, female rats 49 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats >11 000, female rats 6000 mg/kg. Slight skin and eye irritant (rabbits). Inhalation LC 50 for male rats >15 mg/l. Toxicity Class WHO (a.i.) Ib ECOTOXICOLOGY: Birds Acute oral LD 50 for pheasants 92, Japanese quail 68–74 mg/kg. Dietary LC 50 (8 d) for pheasants 1330, quail 11 250 mg/kg diet. Fish LC 50 (96 h) for carp 6, goldfsh 12 mg/l. fospirate Insecticide IRAC 1B NOMENCLATURE: Common name fospirate (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name dimethyl 3,5,6-trichloro-2-pyridyl phosphate Chemical Abstracts name dimethyl 3,4,5-trichloro-2-pyridinyl phosphate CAS RN [5598–52–7] Development codes Dowco 217 Smiles code COP(=O)(OC)Oc1nc(Cl)c(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 306.5 M.f. C 7 H 7 Cl 3 NO 4 P COMMERCIALISATION: History Insecticide introduced by Dow Chemical Co. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Torelle’* (Dow). fosthietan Insecticide, nematicide IRAC 1B NOMENCLATURE: Common name fosthietan (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name diethyl 1,3-dithietan-2-ylidenephosphoramidate (I) Chemical Abstracts name (I); 2-(diethoxyphosphinylimino)-1,3-dithietane CAS RN [21548–32–3] EC no 244–437–7 Development codes AC 64 475 Smiles code CCOP(=O)(OCC)N=C1SCS1 PHYSICAL CHEMISTRY: Mol. wt. 241.3 M.f. C 6 H 12 NO 3 PS 2 Form Tech. is a yellow Supplementary Entries – Extended frontalin 297 liquid, with a mercaptan-like odour. V.p. 0.86 mPa (25 °C) Henry 4.15 × 10 –6 Pa m 3 mol –1 (calc.) S.g./density 1.3 (25 °C) Solubility In water 50 g/l (25 °C). Soluble in acetone, chloroform, methanol, toluene. COMMERCIALISATION: History Insecticide and nematicide described by W. K. Whitney & J. L. Aston (Proc. Br. Insectic. Fungic. Conf. 8th, 1975, 2, 625). Introduced by American Cyanamid Co. Patents US 3476837 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses A broad-range insecticide and nematicide, effective with soil applications of 1–5 kg/ha. Formulation types GR; SL . PRODUCTS: Discontinued products ‘Acconem’* (Cyanamid); ‘Geofos’* (Cyanamid); ‘Nematak’* (USA) (Cyanamid). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 5.7 mg tech./kg. Skin and eye Acute percutaneous LD 50 (24 h) for rabbits 54 mg/kg. Toxicity Class WHO (a.i.) O EC Classifcation T+; R27/28 ENVIRONMENTAL FATE: Soil/Environment In soil DT 50 (chemical degradation)c. 10–42 d. frontalin Insect pheromone See also The Manual of Biocontrol Agents entry: 4:403-4:405 An aggregation pheromone of the Western pine beetle (Dendroctonus brevicomis), the spruce beetle (D. rufpennis), the Douglas fr beetle (D. pseuodtsugae), and the Southern pine beetle (D. frontalis). For a general review, see G. Dupuis & N. Berland, http://www. faidherbe.org/site/cours/dupuis/fronta4.htm. NOMENCLATURE: IUPAC name 1,5-dimethyl-6,8-dioxa-bicyclo[3.2.1]octane Chemical Abstracts name 1,5-dimethyl-6,8-dioxa-bicyclo[3.2.1]octane O (-)-frontalin O CH 3 CH 3 298 The Pesticide Manual Sixteenth Edition © BCPC 2012 furalaxyl CAS RN [28401–39–0] (-)-frontalin, formerly [57917–95–0], [22625–04–3] and [22625–18–9] PHYSICAL CHEMISTRY: Composition The natural pheromone, (-)-frontalin, is the (1S,5R)- isomer (as drawn). Mol. wt. 142.2 M.f. C 8 H 14 O 2 COMMERCIALISATION: Manufacturers ChemTica; Contech APPLICATIONS: Uses In mixture with alpha-pinene, used for control of spruce beetle (Dendroctonus rufpennis) and Douglas fr beetle (Dendroctonus pseudotsugae); also, in mixture with exo-brevocomin and myrcene for control of Western pine beetle (D. brevicomis). Lures are attached to host trees, which attract both male and female beetles. The tree is then felled and destroyed before the insect brood emerges. This reduces attacks in non-baited areas, and reduces the population of beetles. furalaxyl Fungicide FRAC 4, A1 NOMENCLATURE: Common name furalaxyl (BSI, E-ISO, (m) F-ISO) IUPAC name methyl N-(2-furoyl)-N-(2,6-xylyl)-DL-alaninate Chemical Abstracts name methyl N-(2,6-dimethylphenyl)-N-(2-furanylcarbonyl)- DL-alaninate; N-(2,6-dimethylphenyl)-N-(2-furanylcarbonyl)-DL-alanine methyl ester CAS RN [57646–30–7] EC no 260–875–1 Development codes CGA 38 140 (Ciba- Geigy) Smiles code COC(=O)C(C)N(C(=O)c1ccco1)c2c(C)cccc2C PHYSICAL CHEMISTRY: Mol. wt. 301.3 M.f. C 17 H 19 NO 4 Form White, odourless crystals. M.p. 70 °C and 84 °C (dimorphic) V.p. 0.07 mPa (20 °C) K ow logP = 2.7 Henry 9.3 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.22 (20 °C) Solubility In water 230 mg/l (20 °C). In dichloromethane 600, acetone 520, methanol 500, benzene 480, hexane 4 (all in g/kg, 20 °C). Stability Relatively stable in neutral or weakly acidic media. Less stable in alkaline media; on hydrolysis, DT 50 (20 °C) (calc.) >200 d at pH 1 and pH 9, 22 d at pH 10. Stable up to 300 °C. C O O N C CH 3 CH 3 CH 3 CO 2 CH 3 Supplementary Entries – Extended furalaxyl 299 COMMERCIALISATION: History Fungicide reported by F. J. Schwinn et al. (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1977, 42, 1181). Introduced by Ciba-Geigy AG (later Syngenta AG) and frst marketed in 1977. Patents BE 827419; GB 1448810 APPLICATIONS: Biochemistry It is assumed that it inhibits protein synthesis in fungi, by interference with the synthesis of ribosomal RNA. Mode of action Systemic fungicide with protective and curative action. Absorbed through the roots, stalk, and leaves, with translocation. Uses Control of soil-borne diseases caused by Phytophthora and Pythium spp., and other Oomycetes, on ornamentals. Formulation types GR; WP. Compatibility No incompatibility known. PRODUCTS: Discontinued products ‘Fonganil’* (Ciba); ‘Fongarid’* (Syngenta). ANALYSIS: Product analysis by glc. Residues in plants and soils determined by glc with TID (D. J. Caverley & J. Unwin, Analyst (London), 1980, 106, 389). Details available from Syngenta. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 940, mice 603 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3100, rabbits 5508 mg/kg. Weak skin and eye irritant (rabbits). Non- sensitising to skin (guinea pigs). NOEL (90 d) for rats 82 mg/kg daily; for dogs 1.8 mg/ kg b.w. daily. Other Not teratogenic, not mutagenic. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| R52, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 (8 d) for penguin ducks and Japanese quail >6000 mg/kg. LC 50 (8 d) for Japanese quail >6000 ppm. Fish LC 50 (96 h) for rainbow trout 32.5, crucian carp 38.4, guppies 8.7, catfsh 60.0 mg/l. Daphnia LC 50 (48 h) 39.0 mg/l. Algae EC 50 for Scenedesmus subspicatus 27 mg/l. Bees Not toxic to bees when used as directed; LD 50 (24 h, oral) 5 to >20 μg/bee. Worms LC 50 (14 d) for earthworms 510 mg/kg. ENVIRONMENTAL FATE: Animals After oral administration, furalaxyl is rapidly metabolised and eliminated via urine and faeces. The metabolic pathways are independent of sex or dose level administered. Residues in tissues were generally low, and there was no evidence for accumulation or retention of furalaxyl or its metabolites. Plants Furalaxyl is metabolised to polar, water- soluble, partially acidic, probably conjugated, degradation products. Soil/Environment In soil, the compound dissipated with DT 50 31–65 d (20–25 °C). Degradation is by cleavage of the ester bond and by N-dealkylation. 300 The Pesticide Manual Sixteenth Edition © BCPC 2012 furconazole furcarbanil Fungicide NOMENCLATURE: Common name furcarbanil (BSI, E-ISO, (m) F-ISO) IUPAC name 2,5-dimethyl-3-furanilide Chemical Abstracts name 2,5-dimethyl-N-phenyl-3-furancarboxamide CAS RN [28562–70–1] Development codes BAS 319F (BASF) PHYSICAL CHEMISTRY: Mol. wt. 215.3 M.f. C 13 H 13 NO 2 COMMERCIALISATION: History Fungicide evaluated by BASF AG. furconazole Fungicide NOMENCLATURE: Common name furconazole (BSI, E-ISO, (m) F-ISO) IUPAC name (2RS,5RS;2RS,5SR)-5-(2,4-dichlorophenyl)tetrahydro-5-(1H-1,2,4-triazol-1- ylmethyl)-2-furyl 2,2,2-trifuoroethyl ether Chemical Abstracts name 1-[[2-(2,4-dichlorophenyl)tetrahydro-5-(2,2,2- trifuoroethoxy)-2-furanyl]methyl]-1H-1,2,4-triazole CAS RN [112839–33–5] unstated stereochemistry Development codes LS 840 608 (Rhône-Poulenc) Smiles code FC(F)(F)COC1CCC(O1)C(c2ccc(Cl)cc2Cl)n3cncn3 PHYSICAL CHEMISTRY: Mol. wt. 396.2 M.f. C 15 H 14 Cl 2 F 3 N 3 O 2 COMMERCIALISATION: History Fungicide reported by Rhône-Poulenc Agrochimie. APPLICATIONS: Biochemistry Sterol demethylation inhibitor. Mode of action Systemic fungicide with protective and curative action. Uses Control of fungal diseases of fruit and vines. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. Cl OCH 2 CF 3 O CH 2 Cl N N N Supplementary Entries – Extended furconazole-cis 301 furconazole-cis Fungicide NOMENCLATURE: Common name furconazole-cis (BSI, E-ISO, (m) F-ISO) IUPAC name (2RS,5RS)-5-(2,4-dichlorophenyl)tetrahydro-5-(1H-1,2,4-triazol-1- ylmethyl)-2-furyl 2,2,2-trifuoroethyl ether Chemical Abstracts name cis-1-[[2-(2,4-dichlorophenyl)tetrahydro-5-(2,2,2- trifuoroethoxy)-2-furanyl]methyl]-1H-1,2,4-triazole CAS RN [112839–32–4] Development codes LS 840 606 (Rhône-Poulenc) Smiles code FC(F)(F)COC1CCC(O1)C(c2ccc(Cl)cc2Cl)n3cncn3 PHYSICAL CHEMISTRY: Mol. wt. 396.2 M.f. C 15 H 14 Cl 2 F 3 N 3 O 2 Form Colourless crystals. M.p. 86 °C V.p. 0.0145 mPa (25 °C) Solubility In water 21 mg/l. In organic solvents 370–1400 g/l. COMMERCIALISATION: History Fungicide reported by B. Zech et al. (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., 2, 503). Introduced by Rhône-Poulenc Agrochimie. APPLICATIONS: Biochemistry Sterol demethylation inhibitor Mode of action Systemic fungicide with protective and curative action. Uses For control of Ascomycetes, Basidiomycetes, and Fungi Imperfecti (powdery mildew, rust, scab, leaf spot and other foliar pathogens) in fruit, vines, cereals, and tropical crops. Formulation types EC; SC. WP. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 450–900 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Non-irritating to eyes and skin (rabbits). Other Non-mutagenic in micronucleus and Ames assays. Toxicity Class WHO (a.i.) II Cl OCH 2 CF 3 O CH 2 Cl N N N 302 The Pesticide Manual Sixteenth Edition © BCPC 2012 furmecyclox furethrin Insecticide IRAC 3 NOMENCLATURE: IUPAC name (RS)-3-furfuryl-2-methyl-4-oxocyclopent-2-enyl (1RS,2RS;1RS,2SR)- 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate; Roth: (RS)-3-furfuryl- 2-methyl-4-oxocyclopent-2-enyl (1RS)-cis-trans-2,2-dimethyl-3-(2-methylprop-1-enyl) cyclopropanecarboxylate; 3-furfuryl-2-methyl-4-oxycyclopent-2-enyl (±)-cis-trans- chrysanthemate Chemical Abstracts name (±)-3-(2-furanylmethyl)-2-methyl-4-oxo-2- cyclopenten-1-yl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate Other names furethrin CAS RN [17080–02–3], formerly [7076–49–5] Smiles code CC(=CC1C(C(=O)OC/2CC(=O)/C(=C2/C)/Cc3ccco3)C1(C)C)C;without stereochemistry:CC(=CC1C(C(=O)OC2CC(=O)C(=C2C)Cc3ccco3)C1(C)C)C PHYSICAL CHEMISTRY: Mol. wt. 342.4 M.f. C 21 H 26 O 4 Form Pale yellow liquid. B.p. 187–188 °C /0.4 mmHg Solubility Practically insoluble in water. Soluble in refned kerosine. COMMERCIALISATION: History Insecticide (M. Matsui et al., J. Am. Chem. Soc., 1952, 74, 2181). The ester mixture from the (RS)- alcohol and the (1R)-trans- acid is a more potent insecticide than the complete mixture of stereoisomers (W. A. Gersdorff & N. Mitlin, J. Econ. Entomol., 1952, 45, 849). APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. Mode of action Contact insecticide. Uses An insecticide giving a rapid ‘knockdown’ of Musca domestica. furmecyclox Fungicide NOMENCLATURE: Common name furmé(cyclox) ((m) F-ISO); furmecyclox (BSI, E-ISO) IUPAC name methyl N-cyclohexyl-2,5-dimethyl-3-furohydroxamate; methyl N-cyclohexyl- 2,5-dimethylfuran-3-carbohydroxamate Chemical Abstracts name N-cyclohexyl-N-methoxy-2,5-dimethyl-3-furancarboxamide CAS RN [60568–05–0] EC no 262–302–0 Development codes BAS 389F (BASF) Smiles code CON(C1CCCCC1)C(=O)c2cc(C)oc2C PHYSICAL CHEMISTRY: Mol. wt. 251.3 M.f. C 14 H 21 NO 3 Form Crystalline solid. M.p. 33 °C V.p. 8.4 mPa (20 °C) Henry 7.04 × 10 –3 Pa m 3 mol –1 (calc.) Solubility In Supplementary Entries – Extended furophanate 303 water 0.3 g/l (20 °C). In acetone, chloroform, ethanol >1 kg/kg. Stability Decomposed by sunlight and hydrolysed under strongly acidic and strongly alkaline conditions. COMMERCIALISATION: History Fungicide reported by E-H. Pommer & B. Zeeh (Pestic. Sci., 1977, 8, 320). Introduced by BASF AG. Patents DE 2455082; GB 1517960; US 3993772 APPLICATIONS: Uses Used as a seed treatment for cereals, cotton (against Rhizoctonia solani), potatoes and other crops. Also to protect wood against fungal decay. Formulation types DS; Wet treatment. PRODUCTS: Discontinued products ‘Campogran’* (BASF); ‘Epic’* (Gustafson); ‘XyligenB’* (BASF). ANALYSIS: Product analysis by hplc. Residues determined by glc with FID. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3780 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Potential skin irritant.. Toxicity Class WHO (a.i.) U EC Classifcation R40| N; R50, R53 furophanate Fungicide NOMENCLATURE: Common name furophanate (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name methyl 4-(2-furfurylideneaminophenyl)-3-thioallophanate Chemical Abstracts name methyl [[[2-[(2-furanylmethylene)amino]phenyl]amino] thioxomethyl]carbamate CAS RN [53878–17–4] Development codes RH-3928 Smiles code COC(=O)NC(=S)Nc1ccccc1N=Cc2ccco2 PHYSICAL CHEMISTRY: Mol. wt. 303.3 M.f. C 14 H 13 N 3 O 3 S COMMERCIALISATION: History Fungicide evaluated by Rohm & Haas Co. 304 The Pesticide Manual Sixteenth Edition © BCPC 2012 gliotoxin furyloxyfen Herbicide NOMENCLATURE: Common name furyloxyfè(ne) ((m) F-ISO); furyloxyfen (BSI, E-ISO) IUPAC name (±)-5-(2-chloro-α,α,α-trifuoro-p-tolyloxy)-2-nitrophenyl tetrahydro-3-furyl ether Chemical Abstracts name (±)-3-[5-[2-chloro-4-(trifuoromethoxy)phenoxy]-2- nitrophenoxy]tetrahydrofuran CAS RN [80020–41–3] unstated stereochemistry Development codes MT-124 (Mitsui Toatsu) Smiles code [O-][N+](=O)c1ccc(Oc2ccc(c(Cl)c2)C(F)(F)F)cc1OC3CCOC3 PHYSICAL CHEMISTRY: Mol. wt. 403.7 M.f. C 17 H 13 ClF 3 NO 5 COMMERCIALISATION: History Herbicide developed by Mitsui Toatsu Chemicals, Inc. APPLICATIONS: Biochemistry Protoporphyrinogen inhibitor. gliotoxin Fungicide NOMENCLATURE: Common name gliotoxin () IUPAC name (3R,5aS,6S,10aR)-2,3,5a,6,10,10-hexahydro-6-hydroxy-3-hydroxymethyl-2- methyl-3,10a-epidithiopyrazino[1,2-a]indole-1,4-dione Chemical Abstracts name [3R-(3α,5aβ,6β,10aα)]-2,3,5a,6-tetrahydro-6-hydroxy- 3-(hydroxymethyl)-2-methyl-10H-3,10a-epidithiopyrazino[1,2-a]indole-1,4-dione CAS RN [67–99–2] Smiles code CN1C(=O)C23CC4=CC=CC(O)C4N3C(=O) C1(CO)SS2 PHYSICAL CHEMISTRY: Mol. wt. 326.4 M.f. C 13 H 14 N 2 O 4 S 2 M.p. 221 °C (decomp.) Solubility In water 700 mg/l (30 °C). Moderately soluble in acetic acid, acetone, chloroform, ethanol, methanol. Stability Easily oxidised and is inactivated in 10 min at 100 °C; it is fairly stable in aqueous acids, but is rapidly inactivated in neutral or alkaline solutions. Specifc rotation [α]25D –290° (800 mg/l ethanol) CF 3 O O NO 2 Cl O Supplementary Entries – Extended glyodin 305 COMMERCIALISATION: Production Formed in cultures of Trichoderma viride, Gliocladium fmbriatum, Aspergillus fumigatum and several Penicillium spp. History Antifungal antibiotic isolated by R. Weindling & O. H. Emerson (Phytopathology, 1936, 26, 1068) and structure established by M. R. Bell (J. Am. Chem. Soc., 1958, 80, 1001). Instability has limited its use in crop protection. APPLICATIONS: Biochemistry Antifungal antibiotic. Uses It is antifungal, at 4 mg/l inhibiting spore growth of Botrytis allii and at 2 mg/l those of Fusarium coeruleum. MAMMALIAN TOXICOLOGY: Other An intravenous injection of 45 mg/kg was lethal to rabbits (J. R. Johnson et al., ibid., 1943, 65, 2005). glyodin Acaricide, fungicide NOMENCLATURE: Common name glyodin (BSI, E-ISO, (m) F-ISO) IUPAC name 2-heptadecyl-2-imidazoline acetate; acetic acid - 2-heptadecyl-2-imidazoline (1:1) Chemical Abstracts name 2-heptadecyl-4,5-dihydro-1H-imidazolyl monoacetate CAS RN [556–22–9] Development codes Crag Fruit Fungicide 341 Smiles code CCCCCCCCCCCCCCCCCC1=NCC[NH2+]1.CC(=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 368.6 M.f. C 22 H 44 N 2 O 2 Form Light orange crystals. M.p. 62–68 °C S.g./density 1.035 (20 °C) Solubility Practically insoluble in water. In isopropanolc. 390 g/kg; practically insoluble in acetone, toluene. Stability Readily hydrolysed by alkali to N-(2-aminoethyl)heptadecanamide. COMMERCIALISATION: History Fungicide reported by R. H. Wellman & S. E. A. McCallan (Contrib. Boyce Thompson Inst., 1946, 14, 151). Introduced by Union Carbide Corp. Patents GB 598927; US 2540170; US 2540171 APPLICATIONS: Mode of action Protective fungicide and acaricide. Uses Sprays, after addition of calcium carbonate to give the free base, were used to protect foliage from attack by fungi. Formulation types SL . Compatibility Incompatible with oils or EC formulations. PRODUCTS: Discontinued products ‘CragFungicide 341’* (Union Carbide). ANALYSIS: Residues determined by spectrometry (AOAC Methods 18th Ed., 963.23) or by titration with an anionic surfactant (E. F. Hillenbrand et al., Anal. Chem., 1951, 23, 626). 306 The Pesticide Manual Sixteenth Edition © BCPC 2012 glyphosate-trimesium MAMMALIAN TOXICOLOGY: NOEL In feeding trials, dogs tolerated 71 mg a.i. (as formulation)/kg diet; guinea-pigs tolerated 153 mg/kg diet; rats tolerated 91 mg/kg diet (C. P. Carpenter, Arch. Ind. Hyg. Occup. Med., 1951, 4, 494). Toxicity Class WHO (a.i.) O glyphosate-trimesium Herbicide HRAC G WSSA 9 The trimethylsulfonium salt of glyphosate. NOMENCLATURE: IUPAC name trimethylsulfonium N-(phosphonomethyl)glycinate Chemical Abstracts name N-(phosphonomethyl)glycine trimethylsulfonium salt Other names sulfosate CAS RN [81591–81–3] Development codes SC.224; ICIA0224 (ICI) PHYSICAL CHEMISTRY: Mol. wt. 245.2 M.f. C 6 H 16 NO 5 PS Form White solid. M.p. Decomp. 150 °C V.p. <0.01 mPa (20 °C) K ow logP = –2.9 Henry <2 × 10-9 Pa m 3 mol –1 (calc.) S.g./density 1.42 Solubility In water >1000 g/l. In acetone, chlorobenzene, ethanol, kerosene, xylene <5 (all in g tech./l). COMMERCIALISATION: History This discontinued salt of glyphosate introduced in Spain (1989) by ICI Agrochemicals (later Syngenta AG). PRODUCTS: Discontinued products ‘Coloso’* (Syngenta); ‘Ouragan’* (Syngenta); ‘Touchdown’* (Syngenta); ‘Toupan’* (Syngenta); ‘Zapp’* (Syngenta); Discontinued mixtures ‘Allzett’* (+ diquat dibromide) (Otsuka). ANALYSIS: Residues by gc/FPD (Resid. Anal. Methods), or gc/ms (ibid.); see also Pestic. Anal. Man., II, 180.489. In soil, by gc/NPD (Environ. Chem. Methods). In water, by hplc/FLD (ibid.). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 748, female rats 755, mice 1250 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Inhalation LC 50 (4 h) for rats 6.2 mg/l air. NOEL (2 y) for rats 21 mg/kg b.w. No teratogenic effect observed. ADI/RfD (EC) 0.2 mg/kg b.w. [2001]; (EPA) 0.1 mg/kg b.w. [1994]. EC Classifcation Xn; R22| N; R51, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail >2050, mallard ducks 950 mg tech./kg. Fish LC 50 (96 h) for trout 1800, bluegill sunfsh >3500 mg/l. Daphnia LC 50 (48 h) 12 mg/l. Algae EC 50 19 mg/l. Bees LD 50 (oral) >0.4 mg/bee; (contact) 0.39 mg/bee. Worms LD 50 (14 d) Supplementary Entries – Extended glyphosine 307 >1000 mg/kg soil. Other benefcial Harmless under feld conditions at feld application rates to parasitic wasps (Aphidius rhopalosiphi), lycosid spiders and carabid beetles (Pterostichus melanarius) (IOBC). glyphosine Plant growth regulator NOMENCLATURE: Common name glyphosine (BSI, E-ISO, (f) F-ISO, ANSI) IUPAC name N,N-bis(phosphonomethyl)glycine (I) Chemical Abstracts name (I) CAS RN [2439–99–8] EC no 219–468–4 Development codes CP 41 845 (Monsanto) Smiles code OC(=O)CN(CP(=O)(O)O)CP(=O)(O)O PHYSICAL CHEMISTRY: Mol. wt. 263.1 M.f. C 4 H 11 NO 8 P 2 Form Colourless solid. M.p. 200 °C (decomp.) V.p. <1.33 × 10 –4 mPa (100 °C) S.g./density 1.8 Solubility In water 350 g/l (20 °C). Insoluble in benzene; very slightly soluble in ethanol. Stability Stable to light. F.p. Non-fammable COMMERCIALISATION: History Increase in carbohydrate deposition in sugar cane described by C. A. Porter & L. E. Ahlrichs (Hawaii Sugar Tech. Rep. 1971, 1972, 30, 71). Plant growth regulator introduced by Monsanto Co. Patents US 3556762 Manufacturers CCA Biochemical APPLICATIONS: Mode of action Absorbed by foliage and translocated throughout the plant especially to growing points. Uses A plant growth regulator used to hasten ripening of sugar cane and to increase the sucrose content. Effective rates are 2.4–4.5 kg/ha. It was removed from the juice during processing. Formulation types SP. PRODUCTS: Discontinued products ‘Polaris’* (Monsanto). ANALYSIS: Residues determined by glc of a derivative by FPD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 7200 mg tech./kg. Skin and eye Non-irritant to skin and corrosive to eyes (rabbits). NOEL In 2 y feeding trials, no adverse effect was observed at rates up to 300 mg/kg diet in dogs, or 10 000 mg/kg diet in rats, and reproduction was not affected. In 1.5 y trials, mice receiving 10 000 mg/kg diet showed no effect and no signifcant tumour frequency. Toxicity Class WHO (a.i.) U EC Classifcation Xi; R41 ENVIRONMENTAL FATE: Soil/Environment Inactivated by microbial action in soils, DT 50 c. 60 d. 308 The Pesticide Manual Sixteenth Edition © BCPC 2012 griseofulvin griseofulvin Fungicide NOMENCLATURE: Common name griseofulvin (BSI, E-ISO, BAN, JMAF); grisé(ofulvine) ((f) F-ISO) IUPAC name (2S,6′R)-7-chloro-2′,4,6-trimethoxy-6′-methylspiro[benzofuran-2(3H),1′- cyclohex-2′-ene]-3,4′-dione; 7-chloro-2′,4,6-trimethoxybenzofuran-2(3H)-spiro-1′- cyclohex-2′-ene-3,4′-dione Chemical Abstracts name (1′S)-trans-7-chloro-2′,4,6-trimethoxy-6′- methylspiro[benzofuran-2(3H),1′-[2]cyclohexene]-3,4′-dione Other names "curling factor" CAS RN [126–07–8] Smiles code COC1=CC(=O)CC(C)C21Oc3c(C2=O) c(OC)cc(OC)c3Cl PHYSICAL CHEMISTRY: Mol. wt. 352.8 M.f. C 17 H 17 ClO 6 Form Colourless crystals. M.p. 222 °C (subliming from 210 °C) Solubility Practically insoluble in water. In DMSO 120–140 g/l; low solubility in most organic solvents; practically insoluble in petroleum oils. Stability Stable between pH 3.0 and pH 8.8. Specifc rotation [α] +312° (acetone) COMMERCIALISATION: Production Isolated from cultures of Penicillium griseofulvum. History Antifungal antibiotic isolated by A. E. Oxford et al. (Biochem. J., 1939, 33, 240), structure elucidated by J. F. Grove et al. (Chem. Ind. (London), 1955, p. 160; J. Chem. Soc., 1956, p. 3949; Q. Rev. Chem. Soc., 1963, 17, 1). Introduced by Glaxo Ltd, now restricted to veterinary and anthelmintic uses. APPLICATIONS: Biochemistry Antifungal antibiotic. Mode of action A fungicide affecting the morphogenesis of chitinous cell walls (P. W. Brian Ann. Bot. (London), 1949, 13, 59) with some systemic activity (idem, Nature (London), 1951, 167, 347; S. H. Crowdy & D. Pramer, Chem. Ind. (London), 1955, p. 160). Formulation types DP; EC; WP. ANALYSIS: Product analysis by uv spectrometry (G. C. Ashton & A. P. Brown, Analyst (London), 1956, 81, 220). Residues determined by bioassay (P. W. Brian, Trans. Br. Mycol. Soc., 1946, 29, 173). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: IARC 79 (2001). MAMMALIAN TOXICOLOGY: IARC Class 2B Toxicity Class WHO (a.i.) O Supplementary Entries – Extended halosafen 309 halacrinate Fungicide NOMENCLATURE: Common name halacrinate (BSI, E-ISO, (m) F-ISO) IUPAC name 7-bromo-5-chloro-8-quinolyl acrylate Chemical Abstracts name 7-bromo-5-chloro-8-quinolinyl 2-propenoate CAS RN [34462–96–9] Development codes CGA 30 599 Smiles code Clc1cc(Br)c(OC(=O)C=C)c2ncccc12 PHYSICAL CHEMISTRY: Mol. wt. 312.6 M.f. C 12 H 7 BrClNO 2 Form Colourless crystals. M.p. 100–101 °C V.p. 0.08 mPa (20 °C) Henry 4.17 × 10 –3 Pa m 3 mol –1 (calc.) Solubility In water 6 mg/l (20 °C). In benzene 370, dichloromethane 610, methanol 27 (all in g/l, 20 °C). Stability Relatively stable in neutral or slightly acid media but is slowly hydrolysed by alkali. COMMERCIALISATION: History Fungicide reported by J. M. Smith et al. (Proc. Br. Insectic. Fungic. Conf., 8th, 1975, 2, 421). Evaluated by Ciba-Geigy AG. Patents CH 528214; GB 1324296 APPLICATIONS: Mode of action Protective and curative fungicide. Uses It was used, in mixture with captafol, to control Erysiphe graminis and Septoria spp. at 0.5–0.75 kg/ha. PRODUCTS: Discontinued mixtures ‘Tilt’* (+ captafol) (Ciba-Geigy). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3170 mg/kg. Toxicity Class WHO (a.i.) O halosafen Herbicide HRAC E WSSA 14; diphenyl ether NOMENCLATURE: Common name halosafen (BSI, ANSI, E-ISO); halosafè(ne) ((m) F-ISO) IUPAC name 5-(2-chloro-α,α,α,6-tetrafuoro-p-tolyloxy)-N-ethylsulfonyl-2- nitrobenzamide Chemical Abstracts name 5-[2-chloro-6-fuoro-4-(trifuoromethyl)phenoxy]-N- (ethylsulfonyl)-2-nitrobenzamide CAS RN [77227–69–1] Smiles code CCS(=O)(=O) NC(=O)c1cc(Oc2c(F)cc(cc2Cl)C(F)(F)F)ccc1[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 470.8 M.f. C 16 H 11 ClF 4 N 2 O 6 S 310 The Pesticide Manual Sixteenth Edition © BCPC 2012 HC-252 COMMERCIALISATION: History Herbicide evaluated by ICI Agrochemicals. APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. haloxydine Herbicide NOMENCLATURE: Common name haloxydine (BSI, E-ISO, (f) F-ISO) IUPAC name 3,5-dichloro-2,6-difuoropyridin-4-ol Chemical Abstracts name 3,5-dichloro-2,6-difuoro-4-pyridinol CAS RN [2693–61–0] Development codes PP493 Smiles code Oc1c(Cl)c(F)nc(F)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 200.0 M.f. C 5 HCl 2 F 2 NO COMMERCIALISATION: History Herbicide evaluated by ICI Plant Protection Division (later ICI Agrochemicals). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O HC-252 Herbicide NOMENCLATURE: IUPAC name ethyl O-[2-chloro-5-(2-chloro-α,α,α-trifuoro-p-tolyloxy)benzoyl]-L-lactate Other names ethoxyfen-ethyl (non-approved name) CAS RN [131086–42–5] Development codes HC-252 (Budapest Chemical) Smiles code CCOC(=O)[C@@H] (C)OC(=O)c1cc(Oc2ccc(cc2Cl)C(F)(F)F)ccc1Cl;without stereochemistry:CCOC(=O) C(C)OC(=O)c1cc(Oc2ccc(cc2Cl)C(F)(F)F)ccc1Cl PHYSICAL CHEMISTRY: Mol. wt. 451.2 M.f. C 19 H 15 Cl 2 F 3 O 5 (for ethyl ester) Form Brown, oily, viscous liquid (tech.). Solubility Very soluble in acetone, methanol and xylene. F 3 C Cl O Cl C CO 2 CH 2 CH 3 O O C CH 3 H Supplementary Entries – Extended heptachlor 311 COMMERCIALISATION: History Herbicide reported by J. Bakos et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1991, 1, 83). Manufacturers Budapest Chemical APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor; acts by tetrapyrrole and protoporphyrin accumulation. Tetrapyrroles are photosensitisers which cause photo- oxidation, leading to leaf necrosis and plant death. Mode of action Contact herbicide. Uses Control of broad-leaved weeds in winter wheat, winter barley, peas, soya beans and peanuts. Formulation types EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 843, female rats 963, male mice 1269, female mice 1113 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000, rabbits >2000 mg/kg. Non-irritating to skin; moderate eye irritant (rabbits). Inhalation LC 50 (14 d) for male rats 9679, female rats 9344 mg/m 3 air. Other Non-mutagenic in Salmonella micronucleus test, in vitro chromosome aberration test, and in vitro mouse medulla micronucleus test. ENVIRONMENTAL FATE: Soil/Environment Since HC-252 is a contact herbicide, there is no soil residual effect, and no soil persistence problems for following crops. heptachlor Insecticide IRAC 2A NOMENCLATURE: Common name heptachlor (BSI, E-ISO, ESA, JMAF); heptachlore ((m) F-ISO) IUPAC name 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene Chemical Abstracts name 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano- 1H-indene CAS RN [76–44–8] EC no 200–962–3; 213–831–0 heptachlor epoxide Development codes E 3314; Velsicol 104 Smiles code ClC1C=CC2C1C3(Cl)C(=C(Cl) C2(Cl)C3(Cl)Cl)Cl PHYSICAL CHEMISTRY: Composition Tech. grade isc. 72% heptachlor and 28% related compounds. Mol. wt. 373.3 M.f. C 10 H 5 Cl 7 Form Crystalline solid; (tech., waxy solid). M.p. 95–96 °C; (tech. 55–60 °C) B.p. 135–145 °C V.p. 53 mPa (25 °C, pure) Cl Cl Cl Cl Cl Cl Cl 312 The Pesticide Manual Sixteenth Edition © BCPC 2012 heptachlor K ow logP = 4.4–5.5 (Agchem. Desk Ref.) Henry 3.53 × 10 2 Pa m 3 mol –1 (calc.) S.g./density 1.58 (20 °C) (tech.) Solubility In water 0.056 mg/l (25–29 °C). Soluble in many organic solvents, e.g. in acetone 75, benzene 106, xylene 102, cyclohexanone 119, carbon tetrachloride 113, ethanol 4.5 (all in g/100 ml). Tech. in cyclohexanone 1.65 kg/l, ethanol 62.5 g/l, deodorised kerosene 263 g/l, xylene 1.41 kg/l (20–30 °C). Stability Stable in daylight, air, moisture, and moderate heat (up to 160 °C). Not readily dehydrochlorinated, but is susceptible to epoxidation. Hydrolysis DT 50 4.3 d (pH 5), 4.5 d (pH 6, 7), 3.0 d (pH 8) (all 25 °C) (cited in Agchem. Desk Ref.). COMMERCIALISATION: History It was isolated from tech. chlordane, and its insecticidal properties reported by W. M. Rogoff & R. L. Metcalf (J. Econ. Entomol., 1951, 44, 910). Introduced by Velsicol Chemical Corp. Patents US 3437664 APPLICATIONS: Biochemistry Antagonist of the GABA receptor-chloride channel complex. Mode of action Non-systemic insecticide with contact, stomach, and some respiratory action. Uses Control of termites, ants, and soil insects in cultivated and uncultivated soils. Applied as a seed treatment, soil treatment, or directly to foliage. Also used for control of household insects. Formulation types DP; EC; GR; WP; Seed treatment. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Drinox’* (Velsicol). ANALYSIS: Product analysis by glc with FID (AOAC Methods, 18th Ed., 968.04) or by determination of a labile chlorine substituent (ibid., 962.07; CIPAC Handbook, 1970, 1, 420; FAO Specifcation (CP/47); Organochlorine Insecticides, 1973). Residues determined by glc, tlc or paper chromatography (AOAC Methods, 18th Ed., 970.52; A. Ambrus et al., J. Assoc. Off. Anal. Chem., 1981, 64, 773; Analyst (London), 1979, 104, 425; H. K. Suzuki et al., Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 73; Man. Pestic. Residue Anal., pp. 5, 6, 8–10, 12, 19; Anal. Methods Residues Pestic., 1988, Part I, M1, M12). In drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). See also Pestic. Anal. Man., I, 104, 204, 208, 302, 303, 504. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 38 (1984). JMPR Mtg. 71 (1994); JMPR Evaln. I 69 (1993), 72 (1994); JMPR Evaln. II 64 (1991). HSG 14 (1988). PDS 19 (1975). ICSC.743 (2003). CICAD 70 (2006). IARC 79 (2001). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EC, as amended by Regulation 850/2004. MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 147–220, guinea pigs 116, mice 68 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 200–2000, rats 119–250 mg/kg. Irritating to eyes; not a skin irritant (rabbits). Inhalation LC 50 (4 h) for rats 2.0–200 mg/l air (aerosol). NOEL The target organ is the liver, with NOEL in rats ≤5 mg/kg diet, and Supplementary Entries – Extended 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol 313 in dogs 0.5–1.0 mg/kg diet. A 3-generation feeding study gave NOEL in rats 7 mg/kg diet, and in dogs (2-generation reproduction study) 1 mg/kg diet. Heptachlor epoxide is not teratogenic in rabbits at 5 mg/kg daily. ADI/RfD (JMPR) 0.0001 mg/kg b.w. (PTDI) [1994]; (EPA) cRfD 0.0005 mg/kg b.w. [1992]. Water GV GV not established (O). Other Animal experiments have indicated that heptachlor is carcinogenic in some mice and rat strains, perhaps acting as a promoter, rather than an initiator, of carcinogenesis (S. S. Epstein, Sci. Total Environ., 1976, 6, 103–154). A committee of the United States National Academy of Sciences ruled that heptachlor is a carcinogen to certain mouse strains. In vitro and in vivo experiments showed that heptachlor is non-mutagenic, and there was also no evidence of teratogenicity in rabbits. Toxicity Class WHO (a.i.) II EPA (formulation) II EC Classifcation T; R24/25| R40| R33| N; R50, R53: (heptachlor epoxide T; R25| R40| R33| N; R50, R53) PIC Yes. ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducklings >2000 mg/kg. Dietary LC 50 (8 d) for bobwhite quail 450–700, Japanese quail 80–95, pheasants 250–275 mg/kg diet. Fish LC 50 (96 h) for rainbow trout 7, bluegill sunfsh 26, fathead minnows 78–130 μ;g/l. ENVIRONMENTAL FATE: Animals The principal metabolites in animals are heptachlor epoxide (found in the tissues, faeces, and urine), and 1-exo-hydroxychlordene epoxide, a hydrophilic metabolite excreted in the urine. There is a strong tendency for the epoxide to accumulate in body fat. Plants In plants, heptachlor epoxide is a metabolite. Soil/Environment In water, heptachlor rapidly undergoes hydrolysis to 1-hydroxychlordene, which then undergoes microbial epoxidation to 1-hydroxy-2,3-epoxychlordene. Similar degradation pathways occur in moist soil. Soil DT 50 9–10 months when used at agricultural rates. 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol Fungicide NOMENCLATURE: IUPAC name 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol Chemical Abstracts name 2-heptadecyl-4,5-dihydro-1H-imidazole- 1-ethanol CAS RN [95–19–2] Development codes Fungicide 337 Smiles code CCCCCCCCCCCCCCCCCC1=NCCN1CCO PHYSICAL CHEMISTRY: Mol. wt. 352.6 M.f. C 22 H 44 N 2 O COMMERCIALISATION: History Fungicide evaluated by Union Carbide Corp. (later Rhône-Poulenc Agrochimie). 314 The Pesticide Manual Sixteenth Edition © BCPC 2012 heptenophos heptafuthrin Insecticide NOMENCLATURE: Common name heptafuthrin (pa ISO) IUPAC name 2,3,5,6-tetrafuoro-4-(methoxymethyl)benzyl (1RS,3RS;1RS,3SR)-2,2- dimethyl-3-[(1Z)-3,3,3-trifuoroprop-1-enyl]cyclopropanecarboxylate Chemical Abstracts name [2,3,5,6-tetrafuoro-4-(methoxymethyl)phenyl] methyl 2,2-dimethyl-3-[(1Z)-3,3,3-trifuoro-1-propen-1-yl]cyclopropanecarboxylate CAS RN [1130296–65–9] Smiles code FC1=C(F)C(COC)=C(F)C(F)=C1COC(C2C(/C([H])=C([H])\C(F)(F)F) C2(C)C)=O PHYSICAL CHEMISTRY: Mol. wt. 414.3 M.f. C 18 H 17 F 7 O 3 heptenophos Insecticide IRAC 1B; organophosphate NOMENCLATURE: Common name heptenophos (BSI, E-ISO, (m) F-ISO) IUPAC name 7-chlorobicyclo[3.2.0]hepta-2,6-dien-6-yl dimethyl phosphate Chemical Abstracts name 7-chlorobicyclo[3.2.0]hepta-2,6-dien-6-yl dimethyl phosphate CAS RN [23560–59–0] EC no 245–737–0 Development codes Hoe 02982 (Hoechst); AE F002982 (AgrEvo) Offcial codes OMS 1845 Smiles code without stereochemistry: COP(=O)(OC)OC1=C(Cl)C2C=CCC21 PHYSICAL CHEMISTRY: Composition Tech. grade is ≥93% pure. Mol. wt. 250.6 M.f. C 9 H 12 ClO 4 P Form Light brown liquid, with odour typical of a phosphate ester. B.p. 64 °C /0.075 mmHg V.p. 65 mPa (15 °C); 170 mPa (25 °C) K ow logP = 2.32 (OECD 117) Henry 5.73 × 10 –5 (20 °C); F F O CH 3 F F O O H 3 C CH 3 H CF 3 H P(OCH 3 ) 2 O Cl O Supplementary Entries – Extended heptenophos 315 2.33 × 10 –4 (25 °C) (both in Pa m 3 mol –1 ) S.g./density 1.28 (20 °C) Solubility In water 2.2 g tech./l (20 °C). Readily miscible with most organic solvents, e.g. in acetone, methanol, xylene >1, hexane 0.13 (all in kg/l, 25 °C). Stability Hydrolysed in acidic and alkaline media. F.p. 165 °C (Cleveland, open); 152 °C (Pensky-Martens, closed) COMMERCIALISATION: History First described under an erroneous structure (CAS RN [34783–40–9], Biul. Inst. Ochr. Rosl., 1971, No. 50, p. 109); insecticidal and acaricidal properties against crop pests reported by R. T. Hewson (Proc. Br. Insectic. Fungic. Conf., 8th, 1975, 2, 697) and against veterinary pests by W. Bonin (ibid., p. 705). Introduced by Hoechst AG. Patents DE 1643608; GB 1194603; US 3600474; US 3705240; US 3810919 (to Ciba-Geigy) APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide with contact, stomach and respiratory action. Readily penetrates the plant tissues, and is rapidly translocated to all parts of the plant, primarily acropetally. Uses An insecticide with quick initial action and short residual effect. It penetrates plant tissue and is rapidly translocated, controlling sucking insects (especially aphids) and certain Diptera in feld and glasshouse crops. Application rates for ‘Hostaquick’ (550 g/l EC): on fruit trees 0.05%, against woolly aphids 0.1%, on vegetables and ornamentals 0.05%, in cereals 0.4–0.5 l/ha, on glasshouse crops 0.05–0.1%. Also effective against ectoparasites (feas, lice, mites and ticks) of cattle, dogs, pigs, sheep and pets. Phytotoxicity Non-phytotoxic when used as directed, except to some varieties of apple, sweet cherry, and rose. Formulation types EC. PRODUCTS: Discontinued products ‘Hostaquick’* (crop protection use) (Aventis); ‘Ragadan’* (veterinary use) (Intervet); Discontinued mixtures ‘Decisquick’* (+ deltamethrin) (Bayer CropScience). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 96–121, dogs 500–1000 mg/kg b.w. daily. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Mild eye irritant. Inhalation LC 50 (4 h) for rats 0.95 mg/l air. NOEL (2 y) for dogs 12, rats 15 mg/kg diet. ADI/RfD (BfR) 0.002 mg/kg b.w. [1997]. Toxicity Class WHO (a.i.) Ib. EC Classifcation T; R25| N; R50, R53| concn. dep. ECOTOXICOLOGY: Birds Acute oral LD 50 for Japanese quail 17–55 mg/kg (depending on carrier and sex) for pure a.i. Fish LC 50 (96 h) for trout 0.056, carp 24 mg/l. Daphnia LC 50 (48 h) 2.2 μg/l. Algae EC 50 (72 h) 20 mg/l. Bees Toxic to bees. Worms LC 50 (14 d) for Eisenia foetida 98 mg/kg dry, artifcial soil. Other benefcial Harmless to Chrysoperla larvae. 316 The Pesticide Manual Sixteenth Edition © BCPC 2012 heptopargil ENVIRONMENTAL FATE: Animals In rats, following oral administration, 90% is excreted in the urine and 6% in the faeces in metabolised form within 6 days. Plants Four days after application to lettuce, the compound is completely metabolised to polar, water-soluble compounds without accumulation of any intermediate. Soil/Environment In soil, rapidly degraded by micro- organisms, DT 50 (feld) 1.4 d, DT90 (feld) 4.6 d, depending on temperature and soil type; no accumulation. In lab. (aerobic), DT 50 <4 h, DT90 40 h (20 °C). Degradation in water phase of water sediment system is very quick, DT 50 27–77 h. heptopargil Plant growth regulator NOMENCLATURE: Common name heptopargil (BSI, E-ISO, (m) F-ISO) IUPAC name (E)-(1RS,4RS)-bornan-2-one O-prop-2-ynyloxime Chemical Abstracts name (±)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one O-2- propynyloxime CAS RN [73886–28–9] Development codes EGYT 2250 Smiles code CC1(C)C2CCC1(C)C(=NOCC#C)C2 PHYSICAL CHEMISTRY: Mol. wt. 205.3 M.f. C 13 H 19 NO Form Pale yellow oil. B.p. 95 °C /1 mmHg S.g./density 0.9867 (20 °C) Solubility In water 1 g/l (20 °C). Miscible with protic and aprotic organic solvents. COMMERCIALISATION: History Plant growth regulator reported by A. Kis-Tamás et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1980, I, 173). Introduced by EGYT Pharmacochemical Works. Patents US 4244888 APPLICATIONS: Biochemistry Acts by chlorophyll stabilization. Uses A crop yield enhancer applied as seed treatment for maize, rice and sugar beet and by pre-emergence or post-emergence applications in beans, alfalfa, maize, peas, sunfowers and various vegetables. Applied at 4–8 g/100 cwt seed, or 0.25–1.0 kg/ha. Formulation types EC; LS . PRODUCTS: Discontinued products ‘Limbolid’* (EGYT). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 2100, female rats 2141 mg/kg. Inhalation LC 50 for rats >1.4 mg/l air. Toxicity Class WHO (a.i.) III CH 3 N H 3 C CH 3 O CH 2 C CH Supplementary Entries – Extended hexachloroacetone 317 ECOTOXICOLOGY: Fish Moderately toxic to fsh. Bees Moderately toxic to bees. Hercules 3944 Fungicide NOMENCLATURE: IUPAC name 5-chloro-4-phenyl-1,2-dithiol-3-one Chemical Abstracts name 5-chloro-4-phenyl-3H-1,2-dithiol-3-one CAS RN [2425–05–0] Development codes Hercules 3944 Smiles code Clc1ssc(=O)c1c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 228.7 M.f. C 9 H 5 ClOS 2 COMMERCIALISATION: History Fungicide reported by W. R. Sitterly (Plant Dis. Rep., 1961, 45, 200). Introduced by Hercules Inc. hexachloroacetone Herbicide NOMENCLATURE: Common name HCA (WSSA); hexachloroacetone (E-ISO); hexachloracetone (F-ISO); all are accepted in lieu of a common name IUPAC name hexachloroacetone Chemical Abstracts name 1,1,1,3,3,3-hexachloro-2-propanone CAS RN [116–16–5] EC no 204–129–5 Development codes GC 1106 Smiles code ClC(Cl)(Cl)C(=O) C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Composition Tech. isc. 85%. Mol. wt. 264.8 M.f. C 3 Cl 6 O Form Pale yellow liquid. B.p. 203.6 °C S.g./density 1.74 Solubility Slightly soluble in water (25 °C). Miscible with aliphatic and aromatic hydrocarbons, chlorobenzene, methanol, isopropanol, vegetable oils. Stability Reacts slowly with water to form chloroform and trichloroacetic acid, a reaction accelerated by alkali. COMMERCIALISATION: History Herbicide introduced by Allied Chemical Corp., Agricultural Division (later Hopkins Chemical Co.). Patents US 2635117; US 2764479 APPLICATIONS: Mode of action Total herbicide. Uses Used in combinations with petroleum oil or other herbicides for total weed control in non-cropped land, at 5.5–22.5 kg/ha. 318 The Pesticide Manual Sixteenth Edition © BCPC 2012 hexafuoroacetone trihydrate PRODUCTS: Discontinued mixtures ‘Urox 379’* (+ bromacil) (Allied). ANALYSIS: Product analysis is by i.r. spectrometry. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male albino rats 1370–1730 mg/kg. Skin and eye Acute percutaneous LD 50 for male albino rabbits 1900–4060 mg/kg. Other It is slightly lachrymatory. Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22| N; R51, R53 hexadecyl cyclopropanecarboxylate Acaricide NOMENCLATURE: IUPAC name hexadecyl cyclopropanecarboxylate (I) Chemical Abstracts name (I) Other names cycloprate* (rejected common name proposal) CAS RN [54460–46–7] Development codes ZR 856; TF-5166 Smiles code CCCCCCCCCCCCCCCCOC(=O)C1CC1 PHYSICAL CHEMISTRY: Mol. wt. 310.5 M.f. C 20 H 38 O 2 COMMERCIALISATION: History Acaricide evaluated by Zoecon Corp. (later Sandoz AG). PRODUCTS: Discontinued products ‘Zardex’* (Sandoz). hexafuoroacetone trihydrate Herbicide, plant growth regulator NOMENCLATURE: IUPAC name (i) hexafuoroacetone trihydrate; (ii) 1,1,1,3,3,3-hexafuoropropane-2,2-diol dihydrate Chemical Abstracts name 1,1,1,3,3,3-hexafuoro-2-propanone; 1,1,1,3,3,3-hexafuoro- 2,2-propanediol CAS RN [34202–69–2] for (i); [677–71–4] for the diol Development codes GC 7887 PHYSICAL CHEMISTRY: Mol. wt. 220.1 M.f. C 3 H 6 F 6 O 4 Form Colourless liquid. B.p.c. 105 °C S.g./density 1.59 Solubility Soluble in water. Insoluble in most organic solvents. COMMERCIALISATION: History Herbicide introduced by Allied Chemical Corp., Agricultural Division (later Hopkins Agricultural Chemical Co.). Patents GB 1026036 Supplementary Entries – Extended hexafurate 319 APPLICATIONS: Mode of action Total herbicide, desiccant and plant growth regulator. Uses At 11–23 kg/ha, controls annual and perennial weeds, and woody plants, on uncropped land. At 11 kg/ha it destroys potato haulm. Formulation types DC. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.057 (hexafuoroacetone; 2000). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male albino rats 176–204 mg/kg. Skin and eye Acute percutaneous LD 50 for male albino rabbits 108–118 mg/kg. hexafurate Herbicide NOMENCLATURE: Common name hexafurate (WSSA) IUPAC name potassium hexafuoroarsenate Chemical Abstracts name potassium hexafuoroarsenate(1-) CAS RN [17029–22–0] Smiles code [K+].F[As-](F)(F)(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 228.0 M.f. AsF 6 K Form Colourless crystals. M.p. 436 °C (decomp.) V.p. Non-volatile. S.g./density 3.29 Solubility In water 210 g/kg (25 °C, endothermic). Stability Resistant to uv radiation and to microbial breakdown. F.p. Non-fammable COMMERCIALISATION: History First prepared by M. C. Marignac (Ann. Chem. Pharm., 1867, 145, 237), evaluated as a herbicide by Pennwalt Corp. and Dow Chemical Co. Patents US 3189428; US 3419382 APPLICATIONS: Mode of action Selective and systemic herbicide, absorbed by the roots. Uses Effective at 2 kg/ha against prickly pear and other Opuntia spp. PRODUCTS: Discontinued products ‘Nopalmate’* (Pennwalt). ANALYSIS: Product analysis by measurement of fuoride by titration with thorium nitrate. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: Arsenic and arsenic compounds are reviewed in EHC 224 (2001). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1200 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >10 000 mg/kg. Moderately irritating to eyes; not irritating to skin (rabbits). NOEL In 90 d feeding trials on rats, no harmful effect was observed at 1000 mg/kg diet. 320 The Pesticide Manual Sixteenth Edition © BCPC 2012 2-hydrazinoethanol Toxicity Class WHO (a.i.) O EC Classifcation Not specifed, but arsenic compounds in general (with exceptions) are assigned T; R23/25| N; R50, R53 (concentration-dependent) hexylthiofos Fungicide NOMENCLATURE: Common name hexylthiofos (BSI, E-ISO, (m) F-ISO) IUPAC name O-cyclohexyl O,S-diethyl phosphorothioate (I) Chemical Abstracts name (I) CAS RN [41495–67–4] unstated stereochemistry Development codes NTN 3318 Smiles code CCOP(=O)(OC1CCCCC1)SCC PHYSICAL CHEMISTRY: Mol. wt. 252.3 M.f. C 10 H 21 O 3 PS COMMERCIALISATION: History Fungicide evaluated by Bayer AG. holosulf Plant growth regulator NOMENCLATURE: Common name holosulf (BSI, E-ISO, (m) F-ISO) IUPAC name 2-chloroethanesulfnic acid (I) Chemical Abstracts name (I) CAS RN [21780–04–1] Development codes HOL 1302 Smiles code OS(=O)CCCl PHYSICAL CHEMISTRY: Mol. wt. 128.6 M.f. C 2 H 5 ClO 2 S COMMERCIALISATION: History Plant growth regulator evaluated by Bayer AG. APPLICATIONS: Biochemistry Ethylene generator. 2-hydrazinoethanol Plant growth regulator NOMENCLATURE: IUPAC name 2-hydrazinoethanol; 2-hydroxyethylhydrazine Chemical Abstracts name 2-hydrazinoethanol Other names BOH CAS RN [109– 84–2] Smiles code NNCCO HOCH 2 CH 2 NHNH 2 Supplementary Entries – Extended hyquincarb 321 PHYSICAL CHEMISTRY: Mol. wt. 76.1 M.f. C 2 H 8 N 2 O Form Colourless liquid. M.p. -70 °C B.p. 110–130 °C /17.5 mmHg Solubility Miscible with water and lower alcohols (room temperature). Stability Stable in the cool and in the dark. Dilute solutions easily oxidised. COMMERCIALISATION: History Introduced as a plant growth regulator by Olin Corp. APPLICATIONS: Uses Used to promote fowering of Bromeliaceae. Formulation types SL . PRODUCTS: Discontinued products ‘Omafora’* (Olin). 1-hydroxy-1H-pyridine-2-thione Bactericide, fungicide NOMENCLATURE: IUPAC name 1-hydroxy-1H-pyridine-2-thione (i); tautomeric with pyridine-2-thiol 1-oxide (ii) Chemical Abstracts name 1-hydroxy-2(1H)-pyridinethione (i); 2-pyridinethiol 1-oxide (ii) CAS RN [1121–30–8] (i); [1121–31–9] (ii); [32255–90–6] manganese(II) derivative; [13463–41–7] zinc derivative Development codes OM 1563 (zinc salt) Smiles code On1ccccc1=S PHYSICAL CHEMISTRY: Mol. wt. 127.2 M.f. C 5 H 5 NOS Stability Forms strongly chelated metal derivatives. COMMERCIALISATION: History Compounds reported by E. Shaw et al. (J. Am. Chem. Soc., 1950, 72, 4362). Various metal salts investigated as fungicides (M. Szkolnik & J. M. Hamilton, Plant Dis. Rep., 1957, 41, 289, 293, 301) and evaluated by the Olin Mathieson Chemical Corp. PRODUCTS: Discontinued products ‘Omadine’* (Olin); ‘Omadine OM1563’* (zinc derivative) (Olin); ‘Omadine OM1564’* (manganese(II) derivative) (Olin); ‘Omadine OM1565’* (iron derivative) (Olin). hyquincarb Insecticide NOMENCLATURE: Common name hyquincarb (BSI, E-ISO, (m) F-ISO) IUPAC name 5,6,7,8-tetrahydro-2-methyl-4-quinolyl dimethylcarbamate Chemical Abstracts name 5,6,7,8-tetrahydro-2-methyl-4-quinolinyl dimethylcarbamate 322 The Pesticide Manual Sixteenth Edition © BCPC 2012 2-imidazolidone CAS RN [56716–21–3] Development codes Hoe 25 682 Smiles code CN(C)C(=O)Oc1cc(C)nc2CCCCc12 PHYSICAL CHEMISTRY: Mol. wt. 234.3 M.f. C 13 H 18 N 2 O 2 COMMERCIALISATION: History Insecticide reported by K-D. Bock (Proc. Br. Crop. Prot. Conf. - Pests Dis., 1977, 3, 1017). Evaluated by Hoechst AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide. Uses For use against aphids. ICIA0858 Fungicide NOMENCLATURE: Chemical Abstracts name N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide CAS RN [112860–04–5] Development codes ICIA0858; SC-0858 Smiles code COc1ccc(NC(=O)C2CC2)cn1 PHYSICAL CHEMISTRY: Mol. wt. 192.2 M.f. C 10 H 12 N 2 O 2 COMMERCIALISATION: History Fungicide evaluated by Zeneca Agrochemicals. APPLICATIONS: Uses Evaluated as a broad-spectrum fungicide. 2-imidazolidone Insecticide NOMENCLATURE: IUPAC name 2-imidazolidone; imidazolidin-2-one Chemical Abstracts name 2-imidazolidinone Other names ethyleneurea CAS RN [120–93–4] Smiles code O=C1NCCN1 PHYSICAL CHEMISTRY: Mol. wt. 86.09 M.f. C 3 H 6 N 2 O Form Colourless needles. M.p. 131–132 °C Solubility Readily soluble in water. COMMERCIALISATION: History Insect growth regulator reported by H. G. Simkover (J. Econ. Entomol., 1964, 57, 574). Evaluated by Shell Development Co. Patents US 3242044 C NH O N OCH 3 Supplementary Entries – Extended inabenfde 323 APPLICATIONS: Mode of action Insect growth regulator. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice >5000 mg/kg. inabenfde Plant growth regulator NOMENCLATURE: Common name inabenfde (BSI, E-ISO, (m) F-ISO) IUPAC name 4′-chloro-2′-(α-hydroxybenzyl)isonicotinanilide Chemical Abstracts name N-[4-chloro-2-(hydroxyphenylmethyl)phenyl]- 4-pyridinecarboxamide CAS RN [82211–24–3] unstated stereochemistry Development codes CGR-811 (Chugai) Smiles code OC(c1ccccc1)c2cc(Cl) ccc2NC(=O)c3ccncc3 PHYSICAL CHEMISTRY: Mol. wt. 338.8 M.f. C 19 H 15 ClN 2 O 2 Form Pale yellow- brown or colourless crystals. M.p. 210–212 °C V.p. 0.063 mPa (20 °C) K ow logP = 3.13 Solubility In water 1 mg/l (30 °C). In acetone 3.6, ethyl acetate 1.43, xylene 0.58, methanol 2.35, ethanol 1.61, chloroform 0.59, DMF 6.72, acetonitrile 0.58, tetrahydrofuran 1.61, hexane 8 × 10 –4 (all in g/l, 30 °C). Stability Stable to heat and sunlight. Slightly unstable in alkaline media; after 2 weeks at 40 °C, hydrolysed 16.2% (pH 2), 49.5% (pH 5), 83.9% (pH 7), 100% (pH 11). COMMERCIALISATION: History Plant growth regulator reported by K. Nakamura (Jpn. Pestic. Inf., 1987, No. 51, p. 23). Introduced in Japan (1986) by Chugai Pharmaceutical Co., Ltd (agrochemical interests now Eiko Kasei Co. Ltd). Patents EP 48998; US 4377407; JP 6341393 Manufacturers Dongbu HiTek; Eiko Kasei APPLICATIONS: Biochemistry Inhibits gibberellin biosynthesis. Mode of action Plant growth regulator which shortens lower internodes and upper leaf blades. Uses Used to increase resistance to lodging in rice, being applied to the soil surface under submerged conditions, at 1.5–2.4 kg/ha. Phytotoxicity Non-phytotoxic to rice. Formulation types GR; WP. N C NH O Cl CH HO 324 The Pesticide Manual Sixteenth Edition © BCPC 2012 ipazine PRODUCTS: Discontinued products ‘Seritard’* (Eiko Kasei). ANALYSIS: Product and residue analysis by hplc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: J. Pestic. Sci., 1988, 13, 391–394. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >15 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and mice >5000 mg/kg. Not a skin or eye irritant (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 (4 h) for rats >0.46 mg/l air. NOEL In 6 mo and 2 y toxicity studies on dogs and rats, no ill-effects were observed. In reproductive toxicity (3 generations) and teratogenicity studies on rats and rabbits, no abnormalities were observed. Other Not mutagenic in Ames assay. Toxicity Class WHO (a.i.) U EPA (formulation) IV ECOTOXICOLOGY: Fish LC 50 (48 h) for carp >30, grey mullet 11 mg/l. Daphnia LC 50 (3 h) >30 mg/l. ENVIRONMENTAL FATE: Animals The major urinary metabolite in the rat is 4-hydroxyinabenfde (H. Kinoshita et al., Xenobiotica, 1987, 17, 925). Plants Metabolised to inabenfde ketone. Soil/Environment Under Japanese paddy feld conditions, DT 50 c. 4 mo. iodobonil Herbicide NOMENCLATURE: Common name iodobonil (BSI, E-ISO, (m) F-ISO) IUPAC name allyl 4-cyano-2,5-di-iodophenyl carbonate; 4-(allyloxycarbonyloxy)-3,5-di- iodobenzonitrile Chemical Abstracts name 4-cyano-2,6-di-iodophenyl 2-propenyl carbonate CAS RN [25671–45–8] Smiles code Ic1cc(C#N)cc(I)c1OC(=O)OCC=C PHYSICAL CHEMISTRY: Mol. wt. 455.0 M.f. C 11 H 7 I 2 NO 3 COMMERCIALISATION: History Herbicide evaluated by C. H. Boehringer Sohn (later Shell Agrar GmbH). ipazine Herbicide NOMENCLATURE: Common name ipazine (BSI, E-ISO, (f) F-ISO, WSSA) Supplementary Entries – Extended IPSP 325 IUPAC name 6-chloro-N 2 ,N 2 -diethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine; 2-chloro-4- diethylamino-6-isopropylamino-1,3,5-triazine Chemical Abstracts name 6-chloro-N,N-diethyl-N′-(1-methylethyl)-1,3,5-triazine-2,4- diamine CAS RN [1912–25–0] Development codes G 30 031 Smiles code CCN(CC)c1nc(Cl)nc(NC(C)C)n1 PHYSICAL CHEMISTRY: Mol. wt. 243.7 M.f. C 10 H 18 ClN 5 COMMERCIALISATION: History Herbicide evaluated by J. R. Geigy S.A. (later Ciba-Geigy AG). PRODUCTS: Discontinued products ‘Gesabal’* (Ciba-Geigy). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O iprymidam Herbicide NOMENCLATURE: Common name iprymidam (BSI, E-ISO, (m) F-ISO) IUPAC name 6-chloro-N4-isopropylpyrimidine-2,4-diamine Chemical Abstracts name 6-chloro-N4-(1-methylethyl)-2,4-pyrimidinediamine CAS RN [30182–24–2] Development codes SAN 52 123H Smiles code CC(C)Nc1cc(Cl)nc(N)n1 PHYSICAL CHEMISTRY: Mol. wt. 186.6 M.f. C 7 H 11 ClN 4 COMMERCIALISATION: History Herbicide evaluated by Sandoz AG. IPSP Insecticide IRAC 1B NOMENCLATURE: Common name IPSP (JMAF) IUPAC name S-ethylsulfnylmethyl O,O-diisopropyl phosphorodithioate P[OCH(CH 3 ) 2 ] 2 S CH 2 S O CH 3 CH 2 S 326 The Pesticide Manual Sixteenth Edition © BCPC 2012 isamidofos Chemical Abstracts name S-[(ethylsulfnyl)methyl] O,O-bis(1-methylethyl) phosphorodithioate CAS RN [5827–05–4] Development codes PSP-204 (Hokko) Smiles code CCS(=O)CSP(=S)(OC(C)C)OC(C)C PHYSICAL CHEMISTRY: Composition Tech. is 90%. Mol. wt. 304.4 M.f. C 9 H 21 O 3 PS 3 Form Yellow liquid (tech.). V.p. 2 mPa (27 °C) (tech.) S.g./density 1.1696 (20 °C, tech.) Solubility In water 1.5 g/l (15 °C). In hexane 71 g/l (20 °C); freely soluble in acetone and xylene. Stability DT 50 (25 °C) 4 d (pH 7), 3 d (pH 9). Stable up to 100 °C. COMMERCIALISATION: History Insecticide reported by D. Murrayama et al. (Mem. Fac. Agric. Hokkaido Univ., 1966, 6, 73). Introduced by Hokko Chemical Industry Co., Ltd. Patents JP 531126; US 3408426; GB 1068628 APPLICATIONS: Biochemistry Cholinesterase inhibitor Mode of action Systemic insecticide. Uses Control of aphids on potatoes and other vegetables. Formulation types GR . PRODUCTS: Discontinued products ‘Aphidan’* (Hokko). ANALYSIS: Product by tlc with colorimetric determination. Residues by glc with FPD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 25, male mice 320 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats 28, female mice 1300 mg/kg. Toxicity Class WHO (a.i.) O EC Classifcation T+; R27| T; R25| N; R50, R53| concn. dep. ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 20 mg/l. isamidofos Nematicide NOMENCLATURE: Common name isamidofos (BSI, E-ISO, (m) F-ISO) IUPAC name O-ethyl S-(N-methylcarbaniloylmethyl) N-isopropylphosphoramidothioate Chemical Abstracts name O-ethyl S-[2-(methylphenylamino)-2- oxoethyl] (1-methylethyl)phosphoramidothioate CAS RN [66602–87–7] Development codes Hoe 36 275 Smiles code CCOP(=O)(NC(C)C)SCC(=O)N(C)c1ccccc1 Supplementary Entries – Extended isazofos 327 PHYSICAL CHEMISTRY: Mol. wt. 330.4 M.f. C 14 H 23 N 2 O 3 PS COMMERCIALISATION: History Nematicide evaluated by Hoechst AG. isazofos Insecticide, nematicide IRAC 1B NOMENCLATURE: Common name isazofos (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name O-5-chloro-1-isopropyl-1H-1,2,4-triazol-3-yl O,O-diethyl phosphorothioate Chemical Abstracts name O-[5-chloro-1-(1-methylethyl)-1H-1,2,4-triazol-3- yl] O,O-diethyl phosphorothioate CAS RN [42509–80–8] EC no 255–863–8 Development codes CGA 12 223 Smiles code CCOP(=S)(OCC)Oc1nc(Cl)n(n1)C(C)C PHYSICAL CHEMISTRY: Mol. wt. 313.7 M.f. C 9 H 17 ClN 3 O 3 PS Form Yellow liquid. B.p. 120 °C (36 Pa) V.p. 7.45 mPa (20 °C) K ow logP = 2.99 Henry 1.39 × 10-2 Pa m 3 mol –1 (calc.) S.g./density 1.23 (20 °C) Solubility In water 168 mg/l (20 °C). Miscible with organic solvents, e.g. chloroform, methanol, benzene. Stability Hydrolysed more rapidly in alkalis than in acids; DT 50 (calc.) (20 °C) 85 d (pH 5), 48 d (pH 7), 19 d (pH 9). Decomposes above 200 °C. COMMERCIALISATION: History Insecticide and nematicide reported by D. Dawes et al. (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1974, 39, 727) and F. Bachmann & D. Dawes (ibid., p. 801). Developed by Ciba- Geigy AG (later Novartis Crop Protection AG). Patents BE 792452; GB 1419131; GB 1419132 Manufacturers Novartis APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Nematicide and systemic insecticide with contact and stomach action. Uses A soil-applied nematicide used on bananas (against Radopholus similis and Cosmopolites sordidus), citrus, cotton, beet, maize, rice, vegetables, sugar cane, and in turf against soil-dwelling insects. Phytotoxicity Phytotoxic to potatoes and tobacco. Formulation types EC; GR . PRODUCTS: Discontinued products ‘Brace’* (Ciba-Geigy); ‘Miral’* (Novartis); ‘Triumph’* (Ciba- Geigy); ‘Victor’* (Ciba-Geigy). P(OCH 2 CH 3 ) 2 S N N N (CH 3 ) 2 CH Cl O 328 The Pesticide Manual Sixteenth Edition © BCPC 2012 isobenzan ANALYSIS: Product analysis by glc. Residues determined by glc with TID. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 40–60 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats >3100, female rats 118 mg/kg. Mild skin irritant; very slight eye irritant (rabbits). Inhalation LC 50 (4 h) for rats 0.24 mg/l air. NOEL (90 d) for rats 2 mg/kg diet (0.2 mg/kg daily), for dogs 2 mg/kg diet (0.05 mg/kg daily). ADI/RfD (EPA) 0.00002 mg/kg b.w. [1989]. Toxicity Class WHO (a.i.) Ib EPA (formulation) I EC Classifcation T+; R26| T; R24/25| Xn; R48/20| R43| N; R50, R53 ECOTOXICOLOGY: Birds Toxic to birds. Acute oral LD 50 for mallard ducks 61, bobwhite quail 11.1 mg/kg. LC 50 (8 d) for bobwhite quail 81 ppm. Fish LC 50 (96 h) for bluegill sunfsh 0.01, carp 0.22, trout 0.008–0.019 mg/l. Daphnia LC 50 (48 h) 0.0014 mg/l. Bees Toxic to honeybees. ENVIRONMENTAL FATE: Animals It is extensively metabolised and rapidly excreted, primarily in the urine. No accumulation takes place in the body. Soil/Environment DT 50 10 d (lab.). isobenzan Insecticide IRAC 2A NOMENCLATURE: Common name telodrin (JMAF); isobenzan (BSI, E-ISO, (m) F-ISO) IUPAC name 1,3,4,5,6,7,8,8-octachloro-1,3,3a,4,7,7a-hexahydro-4,7- methanoisobenzofuran (I) Chemical Abstracts name (I) CAS RN [297–78–9] EC no 206–045–4 Development codes SD 4402; WL 1650; CP 14957 Smiles code ClC1OC(Cl)C2C1C3(Cl)C(=C(Cl)C2(Cl)C3(Cl)Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 411.8 M.f. C 9 H 4 Cl 8 O COMMERCIALISATION: History Insecticide evaluated by Shell International Chemical Co. Manufactured in the Netherlands from 1958 to 1965. APPLICATIONS: Biochemistry Antagonist of the GABA receptor-chloride channel complex. PRODUCTS: Discontinued products ‘Telodrin’* (Shell). Supplementary Entries – Extended isocarbamid 329 TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 129 (1991). HSG 61 (1991). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T+; R27/28| N; R50 ENVIRONMENTAL FATE: EHC 129 concluded isobenzan is a signifcant hazard to the environment and to exposed workers. isocarbamid Herbicide NOMENCLATURE: Common name isocarbamid (BSI, E-ISO); isocarbamide ((m) F-ISO, WSSA) IUPAC name N-isobutyl-2-oxoimidazolidine-1-carboxamide Chemical Abstracts name N-(2-methylpropyl)-2-oxo-1-imidazolidinecarboxamide CAS RN [30979–48–7] Development codes BAY MNF 0166 Smiles code CC(C)CNC(=O)N1CCNC1=O PHYSICAL CHEMISTRY: Mol. wt. 185.2 M.f. C 8 H 15 N 3 O 2 Form Colourless crystalline solid. M.p. 95–96 °C V.p. <13000 mPa (50 °C) Solubility In water 1.3 g/l (20 °C). In cyclohexanone 130, dichloromethane 281 (both g/kg, 20 °C). Stability Stable in alkaline and acid media. COMMERCIALISATION: History Herbicide reported by L. Eue et al. (Proc. Br. Weed Control Conf., 10th, 1970, 2, 610). Introduced by Bayer AG. Patents DE 1795117; US 3875180 APPLICATIONS: Mode of action Selective herbicide. Uses A selective herbicide for use in sugar beet and fodder beet at rates of 3–4 kg/ha, in mixture with lenacil, for pre-em. application. PRODUCTS: Discontinued mixtures ‘Merpelan AZ’* (+ lenacil) (Bayer); ‘Terratop’* (+ lenacil) (Bayer). ANALYSIS: Residues determined by glc (H. J. Jarczyk, Pfanz.-Nachr. Bayer (Engl. Ed.), 1974, 27, 130). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats >2500, female dogs >500 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats >500 mg/kg. NOEL (90 d) for rats 800 mg/kg diet, for dogs >5000 mg/kg diet. Toxicity Class WHO (a.i.) U 330 The Pesticide Manual Sixteenth Edition © BCPC 2012 isodrin isocil Herbicide NOMENCLATURE: Common name isocil (BSI, E-ISO, (m) F-ISO, ANSI, WSSA); isoprocil (France, Republic of South Africa) IUPAC name 5-bromo-3-isopropyl-6-methyluracil Chemical Abstracts name 5-bromo-6-methyl-3-(1-methylethyl)-2,4(1H,3H)- pyrimidinedione CAS RN [314–42–1] Development codes DuPont Herbicide 82 Smiles code CC(C)n1c(=O)[nH]c(C)c(Br)c1=O PHYSICAL CHEMISTRY: Mol. wt. 247.1 M.f. C 8 H 11 BrN 2 O 2 Form Colourless solid. M.p. 158–159 °C Solubility In water 2.1 g/l (25 °C). Soluble in alkali, acetone, acetonitrile, ethanol. Stability Stable ≥159 °C but decomposed by concentrated acids. COMMERCIALISATION: History Herbicide reported by H. C. Bucha et al. (Science, 1962, 137, 537). Introduced by E. I. du Pont de Nemours & Co. Patents US 3235357 APPLICATIONS: Biochemistry Photosynthesis inhibitor. Mode of action Total herbicide. Uses At 13–18 kg/ha, for control of perennial grasses and on non-cropped land. Formulation types WP. PRODUCTS: Discontinued products ‘Hyvar’* (DuPont). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male albino ratsc. 3400 mg/kg. Toxicity Class WHO (a.i.) O isodrin Insecticide IRAC 2A NOMENCLATURE: Common name isodrin (BSI); isodrine ((f) France) IUPAC name (1R,4S,5R,8S)-1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5,8- dimethanonaphthalene Chemical Abstracts name (1α,4α,4aβ,5β,8β,8aβ)-1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a- hexahydro-1,4:5,8-dimethanonaphthalene CAS RN [465–73–6] EC no 207–366–2 Development codes Compound 711; SD-3418 Smiles code ClC1=C(Cl)C2(Cl)C3C4CC(C=C4)C3C1(Cl)C2(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 364.9 M.f. C 12 H 8 Cl 6 Supplementary Entries – Extended isofenphos 331 COMMERCIALISATION: History Insecticide evaluated by Shell International Chemical Co. APPLICATIONS: Biochemistry Antagonist of the GABA receptor-chloride channel complex. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T+; R26/27/28| N; R50, R53| concn. dep. isofenphos Insecticide IRAC 1B NOMENCLATURE: Common name isofenphos (BSI, E-ISO); isophenphos ((m) F-ISO) IUPAC name O-ethyl O-2-isopropoxycarbonylphenyl N-isopropylphosphoramidothioate; isopropyl O-[ethoxy-N-isopropylamino(thiophosphoryl)]salicylate Chemical Abstracts name 1-methylethyl 2-[[ethoxy[(1-methylethyl)amino] phosphinothioyl]oxy]benzoate CAS RN [25311–71–1] EC no 246–814–1 Development codes BAY SRA 12 869; BAY 92114 (Bayer) Smiles code CCOP(=S) (NC(C)C)Oc1ccccc1C(=O)OC(C)C PHYSICAL CHEMISTRY: Mol. wt. 345.4 M.f. C 15 H 24 NO 4 PS Form Colourless oil; (tech. has a characteristic smell). V.p. 0.22 mPa (20 °C); 0.44 mPa (25 °C) K ow logP = 4.04 (21 °C) Henry 4.2 × 10 –3 Pa m 3 mol –1 (20 °C) S.g./density 1.131 (20 °C) Solubility In water 18 mg/l (20 °C). In isopropanol, hexane, dichloromethane, toluene >200 g/l (20 °C). Stability DT 50 for aqueous hydrolysis 2.8 y (pH 4), >1 y (pH 7), >1 y (pH 9) (22 °C). Photodegradation on soil surface in the laboratory is extremely rapid. Under natural light, photodegradation is not so fast. F.p. >115 °C (tech.) COMMERCIALISATION: History Insecticide reported by B. Homeyer (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1974, 39, 789). Introduced by Bayer AG. Patents DE 1668047 Manufacturers Bayer APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide with contact and stomach action. Translocated from roots to a limited extent. Uses Control of cabbage root fies, carrot fies, onion fies, corn rootworms, white grubs, wireworms, and other soil insects in vegetables, oilseed rape, maize, bananas, turf, sugar cane, and other C OPOCH 2 CH 3 S NHCH(CH 3 ) 2 (CH 3 ) 2 CHO O 332 The Pesticide Manual Sixteenth Edition © BCPC 2012 isofenphos crops; and also controls thrips in citrus and onions. Formulation types DS; EC; GR; WP. PRODUCTS: Discontinued products ‘Amaze’* (Bayer CropScience); ‘Oftanol’* (Bayer CropScience); ‘Pryfon’* (Mobay); Discontinued mixtures ‘Oftanol T’* (+ thiram) (Bayer CropScience). ANALYSIS: Product analysis by glc with FID or TCD (CIPAC Handbook, 1988, D, 114; AOAC Methods, 18th Ed., 987.01). Residues determined by glc with FID (Man. Pestic. Residue Anal., p. 6; Anal. Methods Residues Pestic., 1988, Part I, M5, M13; K. Wagner, Pfanz.-Nachr. Bayer (Engl. Ed.), 1976, 29, 67). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Mtg. 65 (1992); JMPR Evaln. I 66 (1992); JMPR Evaln. II 49 (1986). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male and female ratsc. 20, micec. 125 mg/kg. Skin and eye Acute percutaneous LD 50 for male and female ratsc. 70 mg/kg. Slightly irritating to eyes and skin (rabbits). Inhalation LC 50 (4 h) for male ratsc. 0.5 mg/l, female rats 0.3 mg/l air (aerosol). NOEL (2 y) for rats 1 mg/kg diet (0.05 mg/kg b.w.), dogs 2, mice 1 mg/kg diet. ADI/RfD (JMPR) 0.001 mg/kg b.w. [1986]; (EPA) cRfD 0.00008 mg/kg b.w., however subsequent re-evaluation by EPA would lead to a valuec. 0.0003 mg/kg b.w. [1999]. Toxicity Class WHO (a.i.) Ib EPA (formulation) I EC Classifcation T; R24/25| N; R50, R53| concn. dep. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 8.7, mallard ducks 32–36 mg/kg. Dietary LC 50 (5 d) for bobwhite quail 145, mallard ducks 4908 mg/kg diet. Fish LC 50 (96 h) for golden orfe 6.49, bluegill sunfsh 2.2, rainbow trout 3.3 mg/l. Daphnia LC 50 (48 h) 0.0039–0.0073 mg/l. Algae ErC50 for Scenedesmus subspicatus 6.8 mg/l. Bees Toxic to bees. Worms LC 50 for Eisenia foetida 404 mg/kg dry soil. ENVIRONMENTAL FATE: Animals For a study of metabolism in rats and in rat liver microsomal systems, see M. Ueji & C. Tomizawa, J. Pestic. Sci., 1987, 12, 245, 269. Elimination is very quick; almost 95% is excreted within 24 h, in urine and faeces. Plants The most important metabolites are salicylic acid and dihydroxybenzol acid. Soil/Environment Mobility is medium to low. Degradation in different soils is slow. Supplementary Entries – Extended isolane 333 isofetamid Fungicide NOMENCLATURE: Common name isofetamid (pa ISO) IUPAC name N-[1,1-dimethyl-2-(4-isopropoxy-o-tolyl)-2-oxoethyl]-3-methylthiophene-2- carboxamide Chemical Abstracts name N-[1,1-dimethyl-2-[2-methyl-4-(1-methylethoxy) phenyl]-2-oxoethyl]-3-methyl-2-thiophenecarboxamide CAS RN [875915–78–9] Development codes KF–5411 Smiles code O=C(C(C)(C)NC(C1=C(C)C=CS1)=O)C2=CC=C(OC(C)C)C=C2C PHYSICAL CHEMISTRY: Mol. wt. 359.5 M.f. C 20 H 25 NO 3 S isolane Insecticide NOMENCLATURE: Common name isolane ((m) France) IUPAC name 1-isopropyl-3-methylpyrazol-5-yl dimethylcarbamate Chemical Abstracts name 3-methyl-1-(1-methylethyl)-1H-pyrazol-5-yl dimethylcarbamate CAS RN [119–38–0] EC no 204–318–2 Development codes G 23 611 Smiles code CC(C)n1nc(C)cc1OC(=O)N(C)C PHYSICAL CHEMISTRY: Mol. wt. 211.3 M.f. C 10 H 17 N 3 O 2 Form Colourless liquid. B.p. 105–107 °C /0.33 mmHg V.p. 133 mPa (20 °C) S.g./density 1.07 (20 °C) Solubility Miscible with water and most organic solvents. Stability Hydrolysed by concentrated acids or alkali. COMMERCIALISATION: History Insecticide reported by H. Gysin (Proc. 3rd Int. Congr. Phytopharm., Paris, 1952). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). Patents CH 279533; CH 281967; CH 282655 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact, systemic and fumigant insecticide. C H 3 CH 3 O CH 3 CH 3 C H 3 N CH 3 S OH O 334 The Pesticide Manual Sixteenth Edition © BCPC 2012 isomethiozin PRODUCTS: Discontinued products ‘Isolan’* (Ciba-Geigy); ‘Primin’* (Geigy). ANALYSIS: Product analysis by acid hydrolysis and titrimetric estimation of the dimethylamine produced (R. Suter et al., Fresenius’ Z. Anal. Chem., 1955, 147, 173). Residues determined by colorimetry of the dimethylamine produced on hydrolysis (idem, ibid.; S. A. Hall et al., Anal. Chem., 1951, 23, 1866). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 11–50 mg (in aqueous solution)/kg; for mice 9–18 mg/kg. EC Classifcation T+; R27/28 isomethiozin Herbicide NOMENCLATURE: Common name isomethiozin (BSI, E-ISO); isomé(thiozine) ((f) F-ISO) IUPAC name 6-tert-butyl-4-isobutylideneamino-3-methylthio-1,2,4-triazin-5(4H)-one Chemical Abstracts name 6-(1,1-dimethylethyl)-4-[(2-methylpropylidene)amino]-3- (methylthio)-1,2,4-triazin-5(4H)-one CAS RN [57052–04–7] Development codes BAY DIC 1577 Smiles code CSc1nnc(c(=O)n1N=CC(C)C)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 268.4 M.f. C 12 H 20 N 4 OS Form Colourless crystals. M.p. 159.3 °C V.p. 0.047 mPa (20 °C) Henry 1.26 × 10 –3 Pa m 3 mol –1 (calc.) Solubility In water 10 mg/kg (20 °C). In cyclohexanone 103, dichloromethane 152 (both g/kg, 20 °C). COMMERCIALISATION: History Herbicide reported by H. Hack (Mitt. Biol. Bundesanst. Land-Forstwirtsch. Berlin- Dahlem, 1975, 165, 179; Pfanz.-Nachr. Bayer (Engl. Ed.), 1975, 28, 241). Introduced by Bayer AG. Patents GB 1182801. APPLICATIONS: Uses A post-em. herbicide in areas where there is a heavy infestation of grass, also in winter wheat or, in combination with dichlorprop, in spring cereals (H. Hack, Mitt. Biol. Bundesanst. Land-Forstwirtsch. Berlin-Dahlem, 1975, 165, 179; Pfanz.-Nachr. Bayer (Engl. Ed.), 1975, 28, 241; W. Kolbe, ibid., p. 257). Formulation types WP. PRODUCTS: Discontinued products ‘Tantizon’* (Bayer); Discontinued mixtures ‘Tantizon Combi’* (+ dichlorprop) (Bayer); ‘Tantizon DP’* (+ dichlorprop) (Bayer). ANALYSIS: Supplementary Entries – Extended isonoruron 335 Product analysis by i.r. spectrometry. Residues determined by glc with FID (H. J. Jarczyk, ibid., p. 287). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >10 000, mice >2500 mg/kg. NOEL (90 d) for rats 100, dogs 500 mg/kg diet. Toxicity Class WHO (a.i.) U isonoruron Herbicide NOMENCLATURE: Common name isonoruron (BSI, E-ISO, (m) F-ISO) IUPAC name 1,1-dimethyl-3-(perhydro-4,7-methanoinden-1-yl)urea (i) and 1,1-dimethyl- 3-(perhydro-4,7-methanoinden-2-yl)urea (ii) Chemical Abstracts name N,N-dimethyl-N′-(octahydro-4,7-methano-1H-inden-1-yl) urea (i) and N,N-dimethyl-N′-(octahydro-4,7-methano-1H-inden-2-yl)urea (ii); N,N- dimethyl-N′-[octahydro-4,7-methanoinden-1(or 2)-yl]urea (i + ii) CAS RN [28805–78–9], formerly [28346–65–8] (i) + (ii) PHYSICAL CHEMISTRY: Mol. wt. 222.3 M.f. C 13 H 22 N 2 O Form Colourless crystalline powder. M.p. 150–180 °C Solubility In water 220 mg/l (20 °C). In acetone 11, benzene 78, chloroform 138, ethanol 175 (all in g/kg, 20 °C). COMMERCIALISATION: History Herbicide reported by A. Fischer (Abstr. Int. Congr. Plant Prot., 1967, p. 446). Introduced by BASF AG. Patents DE 1200062 APPLICATIONS: Mode of action Selective herbicide. Uses A mixture of isonoruron and brompyrazon was used pre- and post- em. to control Alopecurus myosuroides, Apera spica-venti and annual broad-leaved weeds in winter cereals at 3.4–4.0 kg formulation/ha. A mixture of isonoruron and buturon was used pre-em. for potatoes at 3.4–4.5 kg formulation/ha. PRODUCTS: Discontinued mixtures ‘Basanor’* (+ brompyrazon) (BASF); ‘Basftox’* (+ buturon) (BASF). ANALYSIS: Product analysis of ‘Basftox’ by uv spectrometry to determine buturon, and titration to determine isonoruron. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 500 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2500 mg ‘Basftox’/kg; for rabbits >4000 mg/kg. NOEL No ill-effect was observed in 120 d feeding trials with rats receiving 400 mg/kg diet or with beagle dogs at 1600 mg/kg diet. Toxicity Class WHO (a.i.) O 336 The Pesticide Manual Sixteenth Edition © BCPC 2012 isopolinate isopamphos Fungicide NOMENCLATURE: IUPAC name 3-nonyloxypropylammonium methylphosphonate Other names izopamfos CAS RN [94343–56–3] Smiles code CCCCCCCCCOCCC[NH3+].COP(=O)[O-] PHYSICAL CHEMISTRY: Composition The material is a mixture of nonyl isomers. Mol. wt. 297.4 M.f. C 13 H 32 NO 4 P Form Colourless, viscous oil with an amine-like smell. COMMERCIALISATION: History Fungicide developed by Borsod. APPLICATIONS: Mode of action Protectant and eradicant fungicide with some systemic activity. Uses As a seed dresssing, effective alone or in combination with benzimidazole fungicides against soil borne diseases on wheat or maize. As a foliar spray used against Peronospora spp. and Phytophthora spp. in tobacco, tomatoes and potatoes. Formulation types SD; Water- miscible. PRODUCTS: Discontinued products ‘BF51’* (Borsod). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1700 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 10 000 mg/kg. Inhalation Irritates mucous membranes. isopolinate Herbicide NOMENCLATURE: Common name isopolinate (BSI, E-ISO, (m) F-ISO) IUPAC name S-isopropyl azepane-1-carbothioate Chemical Abstracts name (S)-(1-methylethyl) hexahydro-1H-azepine-1-carbothioate CAS RN [3134–70–1] Development codes R-4574; CH-83 Smiles code CC(C)SC(=O)N1CCCCCC1 PHYSICAL CHEMISTRY: Mol. wt. 201.3 M.f. C 10 H 19 NOS COMMERCIALISATION: History Herbicide evaluated by Chugai Pharmaceutical Co. Ltd. O P CH 3 O O H C 9 H 19 O(CH 2 ) 3 NH 3 Supplementary Entries – Extended isopropalin 337 isopropalin Herbicide NOMENCLATURE: Common name isopropalin (BSI, E-ISO, ANSI, WSSA); isopropaline ((f) F-ISO) IUPAC name 4-isopropyl-2,6-dinitro-N,N-dipropylaniline Chemical Abstracts name 4-(1-methylethyl)-2,6-dinitro-N,N-dipropylbenzenamine CAS RN [33820–53–0] Development codes EL-179 Smiles code CCCN(CCC)c1c(cc(cc1[N+](=O)[O-])C(C)C)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 309.4 M.f. C 15 H 23 N 3 O 4 Form Orange liquid; (tech. is a red-orange liquid). V.p. 1.9 mPa (30 °C) Solubility In water 0.1 mg/l (25 °C). In acetone, hexane, benzene, chloroform, diethyl ether, acetonitrile, methanol >1 (all in kg/l, 25 °C). Stability Stable in feld use, though decomposed by uv light in laboratory studies. F.p. 40.6 °C COMMERCIALISATION: History Herbicide reported by L. R. Guse (Proc. North Cent. Weed Control Conf., 1969, p. 44; G. J. Shoop, ibid., p. 19). Introduced in USA (1972) by Eli Lilly & Co. (later DowElanco). Patents US 3257190 APPLICATIONS: Mode of action Selective herbicide, which affects physiological growth processes associated with seed germination. Uses Control of broad-leaved weeds and grasses in transplanted tobacco, and in direct-seeded tomatoes and capsicums. Applied pre-planting, with soil incorporation at 1–2 kg/ha. Formulation types EC. PRODUCTS: Discontinued products ‘Paarlan’* (DowElanco). ANALYSIS: ANALYSIS: by glc (W. S. Johnson & O. D. Decherer, Anal. Methods Pestic. Plant Growth Regul., 1976, 8, 369). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice and rats >5000 mg tech./kg; for dogs and rabbits >2000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Slightly irritating to skin and eyes (rabbits). NOEL (90 d) for rats and dogs >250 mg/kg diet (15 mg/kg (CH 3 ) 2 CH NO 2 N[(CH 2 ) 2 CH 3 ] 2 NO 2 338 The Pesticide Manual Sixteenth Edition © BCPC 2012 isothioate b.w. for rats). ADI/RfD (EPA) 0.015 mg/kg b.w. [1986]. Toxicity Class WHO (a.i.) U EPA (formulation) IV ECOTOXICOLOGY: Birds Acute oral LD 50 for chickens >2000, mallard ducks >2000, bobwhite quail >1000, Japanese quail >1000 mg/kg. Fish LC 50 (96 h) for goldfsh >0.15, fathead minnows >0.1 mg/l. Bees LD 50 for honeybees 0.011 mg/bee. ENVIRONMENTAL FATE: Plants In plants, there is no translocation of isopropalin or its degradation products to the leaves or fruit, and no signifcant residues or specifc metabolites have been detected. Soil/Environment In soil, isopropalin is strongly adsorbed, with negligible leaching. In soils DT 50 <0.5 y. Micro-organisms are believed to play a role in the degradation, and there is also some loss from volatilisation and from photodecomposition of material remaining on the soil surface. See R. R. Romanowski Weed Sci. 1978, 26, 258. isopyrimol Plant growth regulator NOMENCLATURE: Common name isopyrimol (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name 1-(4-chlorophenyl)-2-methyl-1-pyrimidin-5-ylpropan-1-ol Chemical Abstracts name α-(4-chlorophenyl)-α-(1-methylethyl)-5-pyrimidinemethanol CAS RN [55283–69–7] Smiles code CC(C)C(O)(c1ccc(Cl)cc1)c2cncnc2 PHYSICAL CHEMISTRY: Mol. wt. 262.7 M.f. C 14 H 15 ClN 2 O COMMERCIALISATION: History Plant growth regulator evaluated by Eli Lilly. isothioate Insecticide IRAC 1B NOMENCLATURE: Common name isothioate (BSI, JMAF, E-ISO, (m) F-ISO) IUPAC name S-2-isopropylthioethyl O,O-dimethyl phosphorodithioate Chemical Abstracts name O,O-dimethyl S-[2-[(1-methylethyl)thio] ethyl] phosphorodithioate Other names MITP CAS RN [36614–38–7] Development codes Z-7272 Smiles code COP(=S)(OC)SCCSC(C)C PHYSICAL CHEMISTRY: Mol. wt. 260.4 M.f. C 7 H 17 O 2 PS 3 Form Light yellowish- Supplementary Entries – Extended 2-isovalerylindan-1,3-dione 339 brown liquid, with an aromatic odour. V.p. 293 mPa (20 °C) Solubility In water 97 mg/l (25 °C). COMMERCIALISATION: History Insecticide introduced by Nihon Nohyaku Co., Ltd. Patents JP 624714 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide, also with vapour action. Uses Effective against aphids when used as a seed dressing or when applied to foliage at 1.0–1.5 kg/ha. Formulation types Seed treatment; GR . PRODUCTS: Discontinued products ‘Hosdon’* (Nihon Nohyaku). ANALYSIS: Product analysis by tlc with estimation of the phosphorus in the spots by standard colorimetric methods (T. Nakagawa & M. Kanauchi, Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 75) or by glc (idem, ibid.). Residue analysis by glc with FID (idem, ibid.). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 150–170, mice 50–80 mg/kg. Skin and eye Acute percutaneous LD 50 for male mice 240 mg/kg. Toxicity Class WHO (a.i.) Ib EC Classifcation T; R24/25 isovaledione Fungicide NOMENCLATURE: Common name isovaledione (BSI, E-ISO, (m) F-ISO) IUPAC name 3-(3,5-dichlorophenyl)-1-isovalerylhydantoin Chemical Abstracts name 3-(3,5-dichlorophenyl)-1-(3-methyl-1-oxobutyl)- 2,4-imidazolidinedione CAS RN [70017–93–5] Development codes S-9373 Smiles code CC(C)CC(=O)N1CC(=O)N(C1=O)c2cc(Cl)cc(Cl)c2 PHYSICAL CHEMISTRY: Mol. wt. 329.2 M.f. C 14 H 14 Cl 2 N 2 O 3 COMMERCIALISATION: History Fungicide evaluated by Sumitomo Chemical Co., Ltd. 2-isovalerylindan-1,3-dione Insecticide, rodenticide NOMENCLATURE: IUPAC name 2-isovalerylindan-1,3-dione Chemical Abstracts name 2-(3-methyl-1-oxobutyl)-1H-indene-1,3(2H)-dione Other names PMP CAS RN [83–28–3] 340 The Pesticide Manual Sixteenth Edition © BCPC 2012 isoxachlortole Smiles code CC(C)CC(=O)C1C(=O)c2ccccc2C1=O PHYSICAL CHEMISTRY: Mol. wt. 230.3 M.f. C 14 H 14 O 3 Form Yellow crystalline solid. M.p. 67–68 °C Solubility Practically insoluble in water; soluble in most organic solvents. Alkali metal and ammonium salts are soluble in water. COMMERCIALISATION: History Insecticide reported by L. B. Kilgore et al. (Ind. Eng. Chem., 1942, 34, 494). Introduced by Kilgore Chemical Co. Patents US 2228170 APPLICATIONS: Uses A slow-acting insecticide. Structure-activity of some analogues was discussed by L. B. Kilgore et al., (Ind. Eng. Chem., 1942, 34, 494). PRODUCTS: Discontinued products ‘Valone’* (Kilgore). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 175 (1995). isoxachlortole Herbicide HRAC F2 WSSA 27; isoxazole NOMENCLATURE: Common name isoxachlortole (BSI, E-ISO, (m) F-ISO) IUPAC name 4-chloro-2-mesylphenyl 5-cyclopropyl-1,2-oxazol-4-yl ketone Chemical Abstracts name [4-chloro-2-(methylsulfonyl)phenyl](5-cyclopropyl-4- isoxazolyl)methanone CAS RN [141112–06–3] Development codes RPA 201735 (Rhône-Poulenc) PHYSICAL CHEMISTRY: Mol. wt. 325.8 M.f. C 14 H 12 ClNO 4 S COMMERCIALISATION: History Herbicide evaluated by Rhône-Poulenc. Manufacturers Rhône-Poulenc APPLICATIONS: Biochemistry p-Hydroxyphenyl pyruvate dioxygenase inhibitor. CH 3 SO 2 Cl O N C O Supplementary Entries – Extended isoxapyrifop 341 isoxapyrifop Herbicide NOMENCLATURE: Common name isoxapyrifop (BSI, E-ISO, (m) F-ISO) IUPAC name (RS)-2-[2-(4-(3,5-dichloro-2-pyridyloxy)phenoxy)propionyl]isoxazolidine Chemical Abstracts name (±)-2-[2-[4-[(3,5-dichloro-2-pyridinyl)oxy]phenoxy]-1- oxopropyl]isoxazolidine CAS RN [87757–18–4] Development codes HOK-1566; HOK-868 (both Hokko); RH-0898 (Rohm & Haas) Smiles code CC(Oc1ccc(Oc2ncc(Cl)cc2Cl)cc1)C(=O)N3CCCO3 PHYSICAL CHEMISTRY: Mol. wt. 383.2 M.f. C 17 H 16 Cl 2 N 2 O 4 Form Colourless crystals. M.p. 121–122 °C K ow logP = 3.36 Solubility In water 9.8 mg/l (25 °C). COMMERCIALISATION: History Herbicide reported by H. Ohyama et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1989, 1, 59). Introduced by Hokko Chemical Industry Co., Ltd. Manufacturers Hokko APPLICATIONS: Biochemistry Fatty acid synthesis inhibitor, by inhibition of acetyl CoA carboxylase (ACCase). Inhibits the growth of meristematic tissue. Mode of action Selective systemic herbicide absorbed mainly through the foliage. Uses Post-emergence control of grass weeds including Echinochloa, Brachiaria, Leptochloa, and Digitaria species in rice, and Alopecurus, Setaria, and Alopecurus species in spring wheat and durum wheat. Formulation types SC. WG . MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 500, female rats 1400 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000, for rabbits >2000 mg/kg. Slight irritation to eyes, non- irritating to skin (rabbits). NOEL (1.5 y) for mice 0.02 mg/kg diet daily. Other Non- mutagenic and non-teratogenic (rats and rabbits). Toxicity Class WHO (a.i.) III ECOTOXICOLOGY: Birds Acute oral LD 50 for Japanese quail >5000 mg/kg. Not mutagenic in assays. Fish LC 50 (96 h) for bluegill sunfsh 1.4, rainbow trout 1.3 mg/l. Daphnia LC 50 (6 h) >10 mg/l. ENVIRONMENTAL FATE: Plants Degrades rapidly in crops. Soil/Environment Degrades rapidly in soil to a pyridyloxyphenoxypropionic acid metabolite (PPPA), which in turn degrades more slowly. DT 50 of the a.i. and PPPA in aerobic laboratory studies 1–4 d and 30–90 d respectively. N Cl Cl O O CH CH 3 C O N O 342 The Pesticide Manual Sixteenth Edition © BCPC 2012 isoxathion isoxathion Insecticide IRAC 1B; organophosphate NOMENCLATURE: Common name isoxathion (BSI, JMAF, E-ISO) IUPAC name O,O-diethyl O-5-phenylisoxazol-3-yl phosphorothioate Chemical Abstracts name O,O-diethyl O-(5-phenyl-3-isoxazolyl) phosphorothioate CAS RN [18854–01–8] EC no 242–624–8 Development codes E-48; SI-6711 (Sankyo) Smiles code CCOP(=S)(OCC)Oc1cc(on1)c2ccccc2 PHYSICAL CHEMISTRY: Composition Tech. is >93%. Mol. wt. 313.3 M.f. C 13 H 16 NO 4 PS Form Pale yellow liquid, with an ester-like odour. B.p. 160 °C /0.15 mmHg V.p. <0.133 mPa (25 °C) K ow logP = 3.88 (pH 6.3) S.g./densityc. 1.23 Solubility In water 1.9 mg/l (25 °C). Readily soluble in organic solvents. Stability Unstable to alkalis. Decomposes at 160 °C. F.p. 210 °C COMMERCIALISATION: History Insecticide reported by N. Sampei et al. (Sankyo Kenkyusho Nempo, 1970, 22, 221). Introduced in Japan in 1972 by Sankyo Co., Ltd (agrochemicals interests now Mitsui Chemicals Agro, Inc.). Patents JP 525850 Manufacturers Mitsui Chemicals Agro; Sankyo Agro APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Insecticide with contact and stomach action. Uses Effective against Aphididae, Coccidae, Diaspididae and Margarodidae (at 500–1000 g/ha) in cabbages, citrus and ornamentals; against Agromyzidae, Cicadellidae, Delphacidae, Ephydridae and Pyralidae (at 600–900 g/ha) in paddy rice; against Coleoptera (at 1.2 kg/ha) in turf and trees; and against Noctuidae and Pieridae (at 500–1000 g/ ha) in pome fruit, citrus fruit and vegetables. Formulation types DP; EC; MG; WP. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Karphos’* (Sankyo Agro); ‘Nekiriton K’* (Sankyo Agro); Discontinued mixtures ‘Sanritto Karufosu Funzai’* (+ simeconazole) (Sankyo Agro). ANALYSIS: Product analysis by glc with FID (T. Nakamura & K. Yamaoka, Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 83). Residues determined by glc with FPD or FTD (idem, ibid.). O P(OCH 2 CH 3 ) 2 S N O Supplementary Entries – Extended japonilure 343 TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986), a general review of organophosphorus insecticides. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 242, female rats 180, male mice 112, female mice 137 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Not irritant to skin. Inhalation LC 50 (4 h) for male rats 4.2, female rats 2.0 g/m 3 . NOEL (2 y) for rats 1.2 mg/ kg b.w.; (9 w) for man 0.03 mg/kg b.w. daily. ADI/RfD (FSC) 0.003 mg/kg. Other Non- mutagenic, non-carcinogenic and non-teratogenic, and no adverse effects on reproduction. Toxicity Class WHO (a.i.) Ib EPA (formulation) II EC Classifcation T; R24/25| N; R50, R53 ECOTOXICOLOGY: Birds LD 50 for 7-day-old chickens 21.6, 50-day-old chickens 19.0 mg/kg. Fish LC 50 (48 h) for carp 1.7 mg/l. Daphnia LC 50 (3 h) for D. pulex 0.0052 mg/l. Bees LC 50 (contact) 0.082 μg/bee. ENVIRONMENTAL FATE: Soil/Environment DT 50 in soil 3–7 d. japonilure Insect pheromone See also The Manual of Biocontrol Agents entry: 4:384 The sex pheromone of the Japanese beetle (Popillia japonica). NOMENCLATURE: IUPAC name 5-[(Z)-dec-1-enyl]-(5R)-dihydrofuran-2(3H)-one Chemical Abstracts name (R,Z)-5-(1-decenyl)dihydro-2(3H)-furanone Other names nuranone CAS RN [64726–91–6], formerly [133494–64–1], [77518– 55–9] and [111192–53–1]; [64726–93–8] (S)- isomer Smiles code CCCCCCCC/C=C\ [C@H]1CCC(=O)O1;without stereochemistry:CCCCCCCCC=CC1CCC(=O)O1 PHYSICAL CHEMISTRY: Mol. wt. 224.3 M.f. C 14 H 24 O 2 Form Colourless, oily liquid. B.p. 130–134 °C /0.1 mmHg K ow logP = 0 (EPA Fact Sheet) Solubility In water <0.01% (25 °C). Soluble in aromatic and aliphatic hydrocarbons (EPA Fact Sheet). Stability Stable for 30 d at 50 °C; stable to light (48 h in sun) (EPA Fact Sheet). Specifc rotation [α]D21 –69.0° (c = 1.42, CHCl3) F.p. >200 °C O O H CH 3 (CH 2 ) 7 H 344 The Pesticide Manual Sixteenth Edition © BCPC 2012 jodfenphos COMMERCIALISATION: History First registered in USA in 1979. Manufacturers Ace; Nitto Denko APPLICATIONS: Mode of action Acts as an attractant. Uses Used for trapping Japanese beetle, in combination with a foral lure (phenethyl propionate: eugenol: geraniol in the proportions 3:7:3). MAMMALIAN TOXICOLOGY: Inhalation For rats >1.35 mg/l (aerosol) (EPA Fact Sheet). jodfenphos Acaricide, insecticide, ixodicide IRAC 1B NOMENCLATURE: Common name iodofenphos (BSI, (m) F-ISO, BAN, ESA, Canada, New Zealand); jodfenphos (E-ISO) IUPAC name O-2,5-dichloro-4-iodophenyl O,O-dimethyl phosphorothioate Chemical Abstracts name O-(2,5-dichloro-4-iodophenyl) O,O-dimethyl phosphorothioate CAS RN [18181–70–9] Development codes C 9491 Smiles code COP(=S)(OC)Oc1cc(Cl)c(I)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 413.0 M.f. C 8 H 8 Cl 2 IO 3 PS Form Colourless crystals. M.p. 76 °C V.p. 0.106 mPa (20 °C) Henry <2.19 × 10-2 Pa m 3 mol –1 (calc.) S.g./density 2.0 (20 °C) Solubility In water <2 mg/l (20 °C). In acetone, toluene 450, dichloromethane 810, benzene 610, isopropanol 230, hexane 33, methanol, n-octanol 30 (all in g/l, 20 °C). Stability Extremely stable in neutral, weakly acidic and weakly alkaline media. Hydrolysed by strong acids and alkalis. Tech. stable to >160 °C. COMMERCIALISATION: History Insecticide and acaricide reported by B. C. Haddow & T. G. Marks (Proc. Br. Insectic. Fungic. Conf., 5th, 1969, 2, 531). Introduced by Ciba AG (later Ciba-Geigy AG). Patents BE 672431; GB 1057609 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide and acaricide with contact and stomach action. Uses Control of crawling and fying insects, e.g. P(OCH 3 ) 2 S I Cl Cl O Supplementary Entries – Extended kelevan 345 fies, ants, silverfsh, bedbugs, cockroaches, mosquitoes, mites, lice, ticks, feas, Beetles, etc. in public hygiene, storerooms and warehouses, household use, and animal and poultry houses. Formulation types WP; SC. EC; DP . PRODUCTS: Discontinued products ‘AlFRACon’* (Ciba-Geigy); ‘Elocril’* (Ciba-Geigy); ‘Nuvanol N’* (Ciba-Geigy); ‘Waspex’* (Rentokil). ANALYSIS: Product analysis by glc. Residues determined by glc with ECD or FPD (N. Burkhard & G. Voss, Pestic. Sci., 1972, 3, 183). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). PDS 43 (1980). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2100, mice 3000, rabbits 2000, dogs 3000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000, rabbits >500 mg/kg; slight irritant to skin, not irritant to eyes of rabbits. Inhalation LC 50 (6 h) for rats >0.246 mg/l. NOEL (90 d) for rats 5 mg/kg diet (0.38 mg/kg daily), for dogs 15 mg/kg diet (0.45 mg/kg daily). Toxicity Class WHO (a.i.) U EPA (formulation) III ECOTOXICOLOGY: Birds Non-toxic to birds. Fish LC 50 (96 h) for rainbow trout 0.06–0.10, goldfsh 1.00–1.33, bluegill sunfsh 0.42–0.75 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Animals Following an oral dose of jodfenphos in rats, 92% was eliminated within 24 h. For details of metabolites see F. R. Johannsen and C. Knowles (J. Econ. Entomol. 1970, 63, 693–697). kelevan Insecticide NOMENCLATURE: Common name ké(lé) ((m) F-ISO); kelevan (BSI, E-ISO) IUPAC name ethyl 5-(1,2,3,4,6,7,8,9,10,10-decachloro-5- hydroxypentacyclo[5.3.0.02,6.03,9.04,8]dec-5-yl)-4-oxovalerate; ethyl 5-(1,2,4,5,6,7,8,8,9,10-decachloro-3-hydroxypentacyclo[5.3.02,6.04,10.05,9]dec-3-yl)-4- oxovalerate Chemical Abstracts name ethyl 1,1a,3,3a,4,5,5,5a,5b,6-decachlorooctahydro-2-hydroxy- γ-oxo-1,3,4-metheno-1H-cyclobuta[cd]pentalene-2-pentanoate CAS RN [4234–79–1] Development codes GC-9160 (Allied) Smiles code CCOC(=O)CCC(=O)CC1(O) C2(Cl)C3(Cl)C4(Cl)C1(Cl)C5(Cl)C2(Cl)C3(Cl)C(Cl)(Cl)C45Cl 346 The Pesticide Manual Sixteenth Edition © BCPC 2012 KH-502 PHYSICAL CHEMISTRY: Mol. wt. 634.8 M.f. C 17 H 12 Cl 10 O 4 COMMERCIALISATION: History Insecticide reported by E. E. Gilbert et al. (J. Agric. Food Chem., 1966, 14, 111); development reviewed by H. Maier-Bode (Residue Rev., 1976, 63, 45). Invented by the Allied Chemical Corp. and developed by C. F. Spiess & Sohn. APPLICATIONS: Mode of action Ingested insecticide. Uses Used to control Leptinotarsa decemlineata on potatoes, Meligethes aeneus and Ceutorhynchus spp. (E. E. Gilbert et al., J. Agric. Food Chem., 1966, 14, 111; H. Maier-Bode, Residue Rev., 1976, 63, 45). Formulation types WP. PRODUCTS: Discontinued products ‘Despirol’* (Spiess); Discontinued mixtures ‘Despirol Plus’* (+ mancozeb) (Spiess). ANALYSIS: Residues determined by glc after oxidation to chlordecone (A. Westlake et al., J. Agric. Food Chem., 1970, 18, 159). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 66 (1986). HSG 2 (1987). EU Status (1107/2009) Never notifed to the EU. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 depends critically on the carrier used; for male rats 290->4000, female rats 240–2830, male rabbits 251 mg/kg. NOEL (90 d) for dogs 20–100 mg/kg diet. Toxicity Class WHO (a.i.) O EC Classifcation T; R24| Xn; R22| N; R51, R53 ENVIRONMENTAL FATE: EHC 66 concluded that kelevan should not be used unless indispensable. KH-502 Insecticide NOMENCLATURE: IUPAC name O,O-diethyl O-(1-phenyl-3-trifuoromethyl-1H-pyrazol-5-yl) phosphorothioate Chemical Abstracts name O-[1-phenyl-3-(trifuoromethyl)-1H-pyrazol-5-yl] O,O-diethyl phosphorothioate Other names fupyrazofos (BSI rejected name) O P(OCH 2 CH 3 ) 2 S N N CF 3 Supplementary Entries – Extended leptophos 347 CAS RN [122431–24–7] Development codes KH-502 PHYSICAL CHEMISTRY: Mol. wt. 380.3 M.f. C 14 H 16 F 3 N 2 O 3 PS COMMERCIALISATION: History Insecticide, discovered by KRICT and developed by Sungbo Chemicals Co. Ltd. Registered in S Korea in 1996. APPLICATIONS: Biochemistry Acetylcholinesterase inhibitor. Uses For use against brown plant hopper, green peach aphid and diamond-back moth, on Chinese cabbage. PRODUCTS: Discontinued products ‘SunBong’* (Sungbo). ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 (aerobic) 13.6 d (J-H. Kim et al., Pestic. Sci. (1998) 54 (3) 237). leptophos Insecticide IRAC 1B NOMENCLATURE: Common name leptophos (BSI, E-ISO, (m) F-ISO, ANSI, ESA); MBCP (JMAF) IUPAC name O-4-bromo-2,5-dichlorophenyl O-methyl phenylphosphonothioate Chemical Abstracts name O-(4-bromo-2,5-dichlorophenyl) O-methyl phenylphosphonothioate CAS RN [21609–90–5] EC no 244–472–8 Development codes VCS 506 (Velsicol) Smiles code COP(=S)(Oc1cc(Cl)c(Br)cc1Cl) c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 412.1 M.f. C 13 H 10 BrCl 2 O 2 PS Form Colourless amorphous solid. M.p. 70.2–70.6 °C S.g./density 1.53 (25 °C) Solubility In water 2.4 mg/l (25 °C). In acetone 470, benzene 1300, cyclohexane 142, heptane 59, isopropanol 24 (all in g/l, 25 °C). Stability Stable to acids for prolonged exposure at normal temperature, but is slowly hydrolysed by alkali. COMMERCIALISATION: History Insecticide reported by A. K. Azab (Proc. Br. Insectic. Fungic. Conf., 5th, 1969, 2, 550). Introduced by Velsicol Chemical Corp. Patents US 3459836 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide. Uses The EC is effective against Lepidoptera, e.g. Spodoptera littoralis on cotton at 1.5 kg/ha; also on fruit and vegetables at 100 g/100 l. The GR, at 1.5 kg/ha, controls Ostrinia nubilalis on maize. Formulation types DP; EC; GR; WP. PRODUCTS: Discontinued products ‘Abar’* (Velsicol); ‘Phosvel’* (Velsicol). 348 The Pesticide Manual Sixteenth Edition © BCPC 2012 LS830556 ANALYSIS: Product analysis by i.r. spectrometry or by glc. Residues determined by glc with FPD or TID. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Evaln. 31 (1978). PDS 38 (1979). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male albino ratsc. 50 mg/kg. Phosphonate analogue: 105–133 mg/kg. Skin and eye Acute percutaneous LD 50 for albino rabbits >800 mg/kg. NOEL In 90 d feeding trials, no ill-effect was observed in rats receiving 10 mg/kg diet or dogs 30 mg/kg diet. ADI/RfD (JMPR) Temporary ADI withdrawn [1978]. Other Causes delayed neurotoxicity. Toxicity Class WHO (a.i.) Ia EC Classifcation T; R25, R39/25| Xn; R21| N; R50, R53 lirimfos Insecticide IRAC 1B NOMENCLATURE: Common name lirimfos (BSI, E-ISO, (m) F-ISO) IUPAC name O-6-ethoxy-2-isopropylpyrimidin-4-yl O,O-dimethyl phosphorothioate Chemical Abstracts name O-[6-ethoxy-2-(1-methylethyl)-4-pyrimidinyl] O,O- dimethyl phosphorothioate CAS RN [38260–63–8] Development codes SAN 201I Smiles code CCOc1cc(OP(=S)(OC)OC)nc(n1)C(C)C PHYSICAL CHEMISTRY: Mol. wt. 306.3 M.f. C 11 H 19 N 2 O 4 PS COMMERCIALISATION: History Insecticide evaluated by Sandoz AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. LS830556 Herbicide NOMENCLATURE: IUPAC name ({[mesyl(methyl)carbamoyl]methyl}amino)methylphosphonic acid CH 2 P O OH OH NH CH 2 C O N S O O CH 3 CH 3 Supplementary Entries – Extended lythidathion 349 Chemical Abstracts name [[[2-methyl(methylsulfonyl)amino]-2-oxoethyl]amino] methylphosphonic acid Other names phosametine (withdrawn BSI proposed name) CAS RN [98565–18–5] Development codes LS830 556 (Rhône-Poulenc) Smiles code CN(C(=O)CNCP(=O)(O)O)S(=O)(=O)C PHYSICAL CHEMISTRY: Mol. wt. 260.2 M.f. C 5 H 13 N 2 O 6 PS Form Crystals. M.p. 213–215 °C V.p. <0.267 mPa Solubility In water 45 g/l (20 °C). In acetic acid 20 g/l. Stability Stable at pH <4. COMMERCIALISATION: History Herbicide introduced by Rhône-Poulenc Agrochimie. Patents FR 2549839 APPLICATIONS: Uses Control of grass and broad-leaved weeds in vines, orchards and cereals. Formulation types WG . TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >4000 mg/kg. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail >2150 mg/kg. Fish LC 50 (96 h) for rainbow trout 320 mg/l. lythidathion Insecticide IRAC 1B NOMENCLATURE: Common name lythidathion (BSI, E-ISO, (m) F-ISO) IUPAC name S-5-ethoxy-2,3-dihydro-2-oxo-1,3,4-thiadiazol-3-ylmethyl O,O-dimethyl phosphorodithioate; 3-dimethoxyphosphinothioylthiomethyl-5-ethoxy-1,3,4-thiadiazol- 2(3H)-one Chemical Abstracts name S-[5-ethoxy-2-oxo-1,3,4-thiadiazol-3(2H)-ylmethyl] O,O- dimethyl phosphorodithioate CAS RN [2669–32–1] Development codes GS 12 968 (Ciba-Geigy); NC 2962 (FBC) Smiles code CCOc1nn(CSP(=S)(OC)OC)c(=O)s1 PHYSICAL CHEMISTRY: Mol. wt. 316.4 M.f. C 7 H 13 N 2 O 4 PS 3 COMMERCIALISATION: History Insecticide evaluated by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O 350 The Pesticide Manual Sixteenth Edition © BCPC 2012 mancopper malonoben Acaricide NOMENCLATURE: Common name malonoben (BSI, E-ISO, ANSI, ESA); malonobè(ne) ((m) F-ISO) IUPAC name 2-(3,5-di-tert-butyl-4-hydroxybenzylidene)malononitrile Chemical Abstracts name [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylene] propanedinitrile CAS RN [10537–47–0] Development codes GCP-5126; S 15126 (both Gulf) Smiles code CC(C)(C)c1cc(C=C(C#N)C#N)cc(c1O)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 282.4 M.f. C 18 H 22 N 2 O Form Crystalline solid. M.p. 140–141 °C COMMERCIALISATION: History Acaricide reported by H. Fukashi et al. (Agric. Biol. Chem., 1971, 35, 2003). Evaluated by Gulf Oil Chemicals Co. APPLICATIONS: Biochemistry Uncouples respiratory phosphorylation (S. Muraoka & H. Terada, Biochim. Biophys. Acta, 1972, 275, 271). Mode of action Ingested and contact acaricide. Uses Effective against various mite species (Aculus, Brevipalpus, Eotetranychus, Panonychus, Phyllocoptruta and Tetranychus) on beans, citrus, cotton, pome and stone fruit, nut trees and ornamentals. Formulation types EC; SC. WP. PRODUCTS: Discontinued products ‘GCP 51262 EC’* (Gulf); ‘GCP 512650 W’* (Gulf); ‘GPC 51264 L’* (Gulf). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 87 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rabbits 2000 mg/kg. Toxicity Class WHO (a.i.) O mancopper Fungicide multi-site: alkylenebis(dithiocarbamate) NOMENCLATURE: Common name mancopper (BSI, E-ISO, F-ISO) IUPAC name ethylenebis(dithiocarbamate) mixed metal complex containingc. 13.7% manganese andc. 4% copper Chemical Abstracts name [[1,2-ethanediylbis[carbamodithioato]](2-)]manganese mixture with [[1,2-ethanediylbis[carbamodithioato]](2-)]copper CAS RN [53988–93–5] COMMERCIALISATION: History Fungicide introduced by Rohm & Haas Co. (now Dow AgroSciences). Supplementary Entries – Extended mebenil 351 APPLICATIONS: Biochemistry Non-specifc thiol reactant, inhibiting respiration. Mode of action Fungicide with protective action. Uses Control of downy mildew on vines. Also used as a seed treatment for control of Septoria and Fusarium spp. on cereals. Formulation types WP; Seed treatment. PRODUCTS: Discontinued products ‘Dithane C-90’* (Dow AgroSciences). ANALYSIS: Details from Dow AgroSciences. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 78 (1988) is a general review of dithiocarbamates and their degradation products. EHC 200 (1998) is a general review of copper and copper compounds. JMPR Mtg. 68 (1993); JMPR Evaln. I 69 (1993); JMPR Evaln. II 70 (1993) for ethylenethiourea. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 9600 mg/kg. mazidox Insecticide IRAC 1B NOMENCLATURE: Common name mazidox (BSI, E-ISO, (m) F-ISO) IUPAC name tetramethylphosphorodiamidic azide (I); tetramethylazidophosphonic diamide Chemical Abstracts name (I) CAS RN [7219–78–5] Development codes NC 7 Smiles code CN(C)P(=O)(N=[N+]=[N-])N(C)C PHYSICAL CHEMISTRY: Mol. wt. 177.1 M.f. C 4 H 12 N 5 OP COMMERCIALISATION: History Insecticide evaluated by Pest Control Ltd (became Schering Agrochemicals). APPLICATIONS: Biochemistry Cholinesterase inhibitor. mebenil Fungicide NOMENCLATURE: Common name mebenil (BSI, E-ISO, (m) F-ISO) IUPAC name o-toluanilide 352 The Pesticide Manual Sixteenth Edition © BCPC 2012 mecarbinzid Chemical Abstracts name 2-methyl-N-phenylbenzamide CAS RN [7055–03–0] Development codes BAS 305F; BAS 3050F; BAS 3053F (all BASF) Smiles code Cc1ccccc1C(=O)Nc2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 211.3 M.f. C 14 H 13 NO Form Crystalline solid. M.p. 125 °C V.p. 4.4 × 103 mPa (20 °C) Solubility Soluble in most organic solvents, e.g. acetone, DMF, DMSO, ethanol, methanol, 3,5,5-trimethylcyclohex-2-enone. COMMERCIALISATION: History Fungicide reported by E-H. Pommer and J. Kradel (Proc. Br. Insectic. Fungic. Conf., 5th, 1969, 2, 563). Developed by BASF AG. APPLICATIONS: Uses Effective against Basidiomycetes and for the control of Puccinia spp. on cereals at 1.7–2.5 kg/ha, and for treating seed potatoes against Rhizoctonia spp. at 0.30–0.37 g/kg seed. Formulation types Seed treatment; WP. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 6000 mg/kg. Skin and eye Not a skin irritant. Toxicity Class WHO (a.i.) O mecarbinzid Fungicide NOMENCLATURE: Common name mecarbinzide (BSI before 1984, (m) F-ISO); mecarbinzid (BSI from 1984, E-ISO) IUPAC name methyl 1-(2-methylthioethylcarbamoyl)benzimidazol-2-ylcarbamate Chemical Abstracts name methyl 1-[[[2-(methylthio)ethyl]amino]carbonyl]-1H- benzimidazol-2-ylcarbamate CAS RN [27386–64–7] Development codes BAS 3201F (BASF) Smiles code COC(=O)Nc1nc2ccccc2n1C(=O)NCCSC PHYSICAL CHEMISTRY: Mol. wt. 308.4 M.f. C 13 H 16 N 4 O 3 S COMMERCIALISATION: History Fungicide evaluated by BASF AG. APPLICATIONS: Mode of action Systemic fungicide. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Supplementary Entries – Extended medinoterb acetate; medinoterb 353 mecarphon Insecticide IRAC 1B NOMENCLATURE: Common name mecarphon (BSI, E-ISO, (m) F-ISO) IUPAC name methyl [methoxy(methyl)phosphinothioylthio]acetyl(methyl)carbamate; S-(N-methoxycarbonyl-N-methylcarbamoylmethyl) O-methyl methylphosphonodithioate Chemical Abstracts name methyl 3,7-dimethyl-6-oxo-2-oxa-4-thia-7-aza-3- phosphaoctan-8-oate 3-sulfde; methyl [[methoxy(methylphosphinothioyl)thio]acetyl] methylcarbamate (former 9CI) CAS RN [29173–31–7] Development codes MC 2420 Smiles code COC(=O)N(C)C(=O)CSP(=S)(C)OC PHYSICAL CHEMISTRY: Mol. wt. 271.3 M.f. C 7 H 14 NO 4 PS 2 Form Colourless solid. M.p. 36 °C Solubility In water 300 mg/l (20 °C). Soluble in aromatic hydrocarbons, chlorinated hydrocarbons, ethanol; insoluble in hexane. COMMERCIALISATION: History Insecticide reported by M. Pianka & W. S. Catling (Proc. Int. Congr. Entomol., 13th, Moscow, 1968, 2, 263). Introduced by Murphy Chemical Co. (later DowElanco). Patents GB 1268199 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact insecticide. Uses Effective at 500 mg/l against Hemiptera, including scale insects, Drosophila spp. on pome and stone fruit, citrus and olives. Formulation types EC; WP. ANALYSIS: Product analysis by glc. Residues determined by glc with ECD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 57 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 720 mg/kg. Toxicity Class WHO (a.i.) O medinoterb acetate; medinoterb Herbicide NOMENCLATURE: Common name medinoterb (BSI, E-ISO); mé(dinoterbe) ((m) F-ISO) IUPAC name 6-tert-butyl-2,4-dinitro-m-cresol; 6-tert-butyl-3-methyl-2,4-dinitrophenol Chemical Abstracts name 6-(1,1-dimethylethyl)-3-methyl-2,4-dinitrophenol CAS RN [3996–59–6] medinoterb; [2487–01–6] medinoterb acetate EC no 219–634–6 acetate Development codes P 1488; MC 1488 (both for the acetate) 354 The Pesticide Manual Sixteenth Edition © BCPC 2012 menazon PHYSICAL CHEMISTRY: Mol. wt. 254.2; (acetate 296.3) M.f. C 11 H 14 N 2 O 5 ; (acetate C 13 H 16 N 2 O 6 ) Form Medinoterb acetate is a yellow crystalline solid. M.p. 86–87 °C (acetate) V.p. 53 mPa (40 °C) (acetate) Solubility In water <10 mg/l (room temperature, acetate). The acetate is slightly soluble in hexane; very soluble in acetone, xylene. Stability The acetate is stable, though slowly hydrolysed by alkali (room temperature) and rapidly on heating. COMMERCIALISATION: History Herbicide reported by G. A. Emery et al. (Proc. 2nd EWRC Symp. New Herbic., 1965, p. 141). Introduced by Murphy Chemical Co. (later DowElanco). Patents GB 1080282 APPLICATIONS: Uses Medinoterb acetate is toxic to seedlings and was recommended pre-em. at 0.56–1.1 kg/ha on sugar beet; also on cotton and leguminous crops. Formulation types WP. ANALYSIS: Product analysis by reduction of the nitro groups by titanium(II) sulfate. Residues determined by colorimetry as medinoterb. MAMMALIAN TOXICOLOGY: Oral Medinoterb acetate: Acute oral LD 50 for rats 42, rabbits 80 mg/kg. Skin and eye Medinoterb acetate: Acute percutaneous LD 50 for rats 1300, guinea-pigs >200 mg/kg. NOEL Medinoterb acetate: (90 d) for male rats 1 mg/kg daily, for female rats 1.2 mg/kg daily. Toxicity Class WHO (a.i.) O EC Classifcation T; R25| Xn; R21 (acetate) ECOTOXICOLOGY: Birds Acute oral LD 50 for hens 560 mg/kg (medinoterb acetate). ENVIRONMENTAL FATE: Soil/Environment Decomposed in soil in ≤120 d. menazon Insecticide IRAC 1B NOMENCLATURE: Common name menazon (BSI, E-ISO, F-ISO, JMAF, ESA); azidithion (France) IUPAC name S-4,6-diamino-1,3,5-triazin-2-ylmethyl O,O-dimethyl phosphorodithioate Chemical Abstracts name S-[(4,6-diamino-1,3,5-triazin-2-yl)methyl] O,O-dimethyl phosphorodithioate CAS RN [78–57–9] EC no 201–123–4 Development codes PP175 (ICI) Smiles code COP(=S)(OC)SCc1nc(N)nc(N)n1 PHYSICAL CHEMISTRY: Composition Tech. is 90–95%. Mol. wt. 281.3 M.f. C 6 H 12 N 5 O 2 PS 2 Form Colourless, Supplementary Entries – Extended menazon 355 odourless crystals; (tech. has a mercaptan-like odour). It forms a crystalline hydrochloride. M.p. 160–162 °C (decomp.) V.p. 0.13 mPa (25 °C) Solubility In water 240 mg/l (20 °C). In 2-ethoxyethanol 200, 2-methoxyethanol 250, tetrahydrofurfuryl alcohol 150, ethylene glycol 100 (all in g/kg, room temperature). Stability The solid is stable ≤50 °C, but is unstable under acid (pH <4) or alkaline (pH >8) conditions. COMMERCIALISATION: History Insecticide reported by A. Calderbank (Chem. Ind. (London), 1961, p. 630). Introduced by ICI Plant Protection Division (later ICI Agrochemicals). Patents GB 899701 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide. Uses Mainly as a tuber or seed treatment to protect seedlings, for foliage application, as a soil drench and root dip. Formulation types SC. WP. Compatibility Not compatible with strongly alkaline pesticides, and may be decomposed by the reactive surfaces of some inert fllers. PRODUCTS: Discontinued products ‘Saphicol’* (ICI); ‘Saphizon’* (ICI); ‘Sayfos’* (ICI); Discontinued mixtures ‘Abol X’* (+ gamma-HCH) (ICI). ANALYSIS: Product analysis by oxidation to phosphoric acid, estimated by colorimetry. Residues determined after conversion to phosphoric acid and subsequent colorimetry (A. Calderbank & J. B. Turner, Analyst (London), 1962, 87, 273; A. Calderbank, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 317). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for female rats 1950 mg/kg. Skin and eye Rabbits treated on their shaved backs for 24 h with 500–800 mg/kg suffered no local or systemic toxic effect. NOEL (90 d) for rats 30 mg/kg diet; in a 2 y trial, rats receiving 4000, 1000 or 250 mg/kg diet showed no signifcant effect other than partial inhibition of cholinesterase. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| N; R52, R53 356 The Pesticide Manual Sixteenth Edition © BCPC 2012 mephosfolan mephosfolan Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name mephosfolan (BSI, E-ISO); mé(phospholan) ((m) F-ISO) IUPAC name diethyl 4-methyl-1,3-dithiolan-2-ylidenephosphoramidate; 2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane Chemical Abstracts name diethyl (4-methyl-1,3-dithiolan-2-ylidene)phosphoramidate CAS RN [950–10–7] EC no 213–447–3 Development codes EI 47 470 (Cyanamid) Smiles code CCOP(=O)(OCC)N=C1SCC(C)S1 PHYSICAL CHEMISTRY: Mol. wt. 269.3 M.f. C 8 H 16 NO 3 PS 2 Form Yellow to amber liquid (tech.). B.p. 120 °C /0.001 mmHg K ow logP = 1.045 Solubility In water 57 mg/l (25 °C). Soluble in ethanol, acetone, 1,2-dichloroethane, and benzene. Stability Stable in aqueous solution under neutral conditions. Hydrolysed by acids and alkalis 2>pH>9. COMMERCIALISATION: History Insecticide and acaricide introduced by American Cyanamid Co. Patents GB 974138 Manufacturers Cyanamid APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide with contact and stomach action. Absorbed by the roots and leaves. Uses Control of aphids, thrips, bollWorms, jassids, mites, stem borers, whitefy, and leaf- eating larvae on cotton, fruit, hops, maize, sorghum, rice, sugar cane, potatoes, vegetables, tobacco, etc. Phytotoxicity Cotton foliage may be injured in high-rainfall conditions. Formulation types EC; GR . PRODUCTS: Discontinued products ‘Cytro-Lane’* (Cyanamid). ANALYSIS: Product analysis by uv spectroscopy. Residues determined by glc (N. R. Pasarela & E. J. Orloski, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 231; R. C. Blinn & J. E. Boyd, J. Assoc. Off. Agric. Chem., 1964, 47, 1106). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986), a general review of organophosphorus insecticides. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. P(OCH 2 CH 3 ) 2 O S S N CH 3 Supplementary Entries – Extended mercuric oxide 357 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3.9–8.9 mg tech./kg; for albino mice 11.3 mg/kg. Skin and eye Acute percutaneous LD 50 (24 h) for male albino rabbits 28.7 mg tech./ kg, >5000 mg (as 2% GR)/kg. NOEL In 90 d feeding trials, male albino rats receiving ≤15 mg/kg diet showed a reduction in erythrocyte and brain cholinesterase activity, but there was no signifcant effect on weight gain. Toxicity Class WHO (a.i.) Ia EPA (formulation) I EC Classifcation T+; R27/28| N; R51, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for Japanese quail 12.8 mg/kg. Fish LC 50 (96 h) for rainbow trout 2.1, carp 54.5 mg/l. Bees Toxic to bees; LC 50 (topical) 3.5 μg/bee. mercuric oxide Fungicide, wound protectant NOMENCLATURE: Common name oxyde mercurique (F-ISO, accepted in lieu of a common name); mercuric oxide (E-ISO, accepted in lieu of a common name) IUPAC name mercury(II) oxide; mercury oxide Chemical Abstracts name mercury oxide (HgO) Other names yellow oxide of mercury CAS RN [21908–53–2], formerly [1344–45–2] Smiles code O=[Hg] PHYSICAL CHEMISTRY: Mol. wt. 216.6 M.f. HgO Form Orange-red to bright red powder (yellow when fnely divided). M.p. Decomposes atc. 500 °C Solubility In water 53 mg/l (25 °C). Insoluble in organic solvents. Soluble in dilute acids, forming the corresponding mercury salts. Stability Decomposes on exposure to light. Darkens atc. 400 °C and decomposes into mercury and oxygen atc. 500 °C. COMMERCIALISATION: History Introduced by Sandoz AG (became Novartis Crop Protection AG, who ceased to manufacture or market it). APPLICATIONS: Uses Wound protectant for pruning cuts and other bark injuries, and control of canker, on fruit trees, rubber trees, vines, and ornamental trees and shrubs. Formulation types PA . PRODUCTS: Discontinued products ‘Kankerdood’* (Bayer); ‘Kankertox’* (Ciba); ‘Santar’* (Sandoz, Zeneca). ANALYSIS: Product analysis by colorimetry (CIPAC Handbook, 1970, 1, 514), by titration (AOAC Methods, 18th Ed., 971.04) or by gravimetry (ibid., 922.05). Mercury impurities determined HgO 358 The Pesticide Manual Sixteenth Edition © BCPC 2012 mercurous chloride (CIPAC Handbook, 1994, F, 264). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.981 (2001). CICAD 50 (2003). IARC 58 (1994). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEC as amended by 91/188/EEC. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for rats 18 mg/kg. Extremely poisonous orally to all animals. Toxicity Class WHO (a.i.) Ib EPA (formulation) I EC Classifcation Not specifed, but inorganic mercury generally is assigned T+; R26/27/28| R33| N; R50, R53, concentration- dependent. PIC Yes. ECOTOXICOLOGY: Fish Toxic to fsh. mercurous chloride Fungicide, insecticide NOMENCLATURE: Common name chlorure mercureux (F-ISO, accepted in lieu of a common name); mercurous chloride (E-ISO, accepted in lieu of a common name) IUPAC name mercury(I) chloride; dimercury dichloride Chemical Abstracts name mercury chloride (Hg2Cl 2 ) Other names calomel CAS RN [10112–91–1] Hg2Cl 2 ; [7546–30–7] HgCl EC no 233–307–5 Smiles code Cl[Hg][Hg]Cl PHYSICAL CHEMISTRY: Mol. wt. 472.1 M.f. Cl 2 Hg 2 Form White powder. M.p. Sublimes at 400–500 °C S.g./density 7.15 Solubility In water 2 mg/l (25 °C). Soluble in most organic solvents, and also in cold dilute acids. Stability Decomposes slowly in sunlight. Under aqueous conditions, slowly decomposes to mercury and mercuric chloride (more rapid decomposition in the presence of alkali). COMMERCIALISATION: History Has long been used as an insecticide and, having a lower toxicity to mammals, largely replaced mercuric chloride, as recommended by H. Glasgow (J. Econ. Entomol., 1929, 22, 335). APPLICATIONS: Uses Soil application for control of Delia spp. and Plasmodiophora brassicae in brassicas; and Sclerotium cepivorum in onions. Control of dollar spot and Fusarium patch on turf. Phytotoxicity Phytotoxic to many crops. Formulation types DP; TC. Hg 2 Cl 2 Supplementary Entries – Extended mesoprazine 359 PRODUCTS: Discontinued products ‘Cyclosan’* (Rhône-Poulenc). ANALYSIS: Product analysis by colorimetry (CIPAC Handbook, 1970, 1, 514), by titration (AOAC Methods, 18th Ed., 971.04) or by gravimetry (ibid., 922.05). Mercury impurities determined (CIPAC Handbook, 1994, F, 264). Residues determined by atomic absorption spectrophotometry (AOAC Methods, 14th Ed., 25.131–25.135) or by colorimetry (ibid., 25.138–25.145). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 1 (1976), 86 (1989), both general reviews of mercury and its compounds. ICSC.984 (2000). CICAD 50 (2003). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEC as amended by 91/188/EEC. MAMMALIAN TOXICOLOGY: IARC Class Inorganic mercury compounds classifed 3 Oral Acute oral LD 50 for rats 210 mg/kg. Toxicity Class WHO (a.i.) II EPA (formulation) II EC Classifcation Xn; R22| Xi; R36/37/38| N; R50, R53 PIC Yes. ECOTOXICOLOGY: Fish Toxic to fsh. mesoprazine Herbicide NOMENCLATURE: Common name mesoprazine (BSI, E-ISO, (f) F-ISO) IUPAC name 6-chloro-N 2 -isopropyl-N4-(3-methoxypropyl)-1,3,5-triazine-2,4-diamine Chemical Abstracts name 6-chloro-N-(3-methoxypropyl)-N′-(1-methylethyl)-1,3,5- triazine-2,4-diamine CAS RN [1824–09–5] Development codes G 34 698; CGA 4999 Smiles code COCCCNc1nc(Cl)nc(NC(C)C)n1 PHYSICAL CHEMISTRY: Mol. wt. 259.7 M.f. C 10 H 18 ClN 5 O COMMERCIALISATION: History Herbicide evaluated by J. R. Geigy S.A. (later Ciba-Geigy AG). 360 The Pesticide Manual Sixteenth Edition © BCPC 2012 metamifop mesulfenfos Insecticide IRAC 1B NOMENCLATURE: Common name mé(sulfenfos) ((m) F-ISO); mesulfenfos (BSI, E-ISO) IUPAC name O,O-dimethyl O-4-methylsulfnyl-m-tolyl phosphorothioate Chemical Abstracts name O,O-dimethyl O-[3-methyl-4-(methylsulfnyl)phenyl] phosphorothioate CAS RN [3761–41–9] Development codes BAY S 2281 Smiles code COP(=S)(OC)Oc1ccc(S(=O)C)c(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 294.3 M.f. C 10 H 15 O 4 PS 2 COMMERCIALISATION: History Insecticide evaluated by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Baycid SO’* (Bayer). metamifop Herbicide NOMENCLATURE: Common name mé(tamifop) ((m) F-ISO); metamifop (BSI, E-ISO) IUPAC name (R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]-2′-fuoro-N- methylpropionanilide Chemical Abstracts name (R)-2-[4-[(6-chloro-2-benzoxazolyl)oxy] phenoxy]-N-(2-fuorophenyl)-N-methylpropanamide CAS RN [256412– 89–2] Development codes DBH-129; K-12974 (both Dongbu Hannong) P O O O S S O O,O-dimethyl O-4-methylsulfinyl-m-tolyl phosphorothioate CH 3 O N CH 3 F O O O N Cl Supplementary Entries – Extended metamifop 361 Smiles code C[C@@H](Oc1ccc(Oc2nc3ccc(Cl)cc3o2)cc1)C(=O)N(C) c4ccccc4F;without stereochemistry:CC(Oc1ccc(Oc2nc3ccc(Cl)cc3o2)cc1)C(=O)N(C) c4ccccc4F PHYSICAL CHEMISTRY: Composition ≥96%. Mol. wt. 440.9 M.f. C 23 H 18 ClFN 2 O 4 Form Light brown, odourless, fne granular powder. M.p. 77.0–78.5 °C B.p. Decomposes V.p. 1.51 × 10 –1 mPa (25 °C) K ow logP = 5.45 (pH 7, 20 °C) Henry 6.35 × 10-2 Pa m 3 mol –1 (20 °C) S.g./density 1.39 Solubility In water 6.87 × 10 –4 g/l (pH 7, 20 °C). In acetone, 1,2-dichloroethane, ethyl acetate, methanol and xylene >250, n-heptane 2.32, n-octanol 41.9 (all in g/l, 20 °C). Stability Stable at 54 °C. COMMERCIALISATION: History Reported by T. J. Kim et al. (Proc. BCPC Int. Congr., Glasgow, 2003, 1, 81). Discovered by Korean Research Institute of Chemical Technology (KRICT) and developed by Dongbu Hannong Chemical Co. Ltd (now Dongbu HiTek). Manufacturers Dongbu HiTek APPLICATIONS: Biochemistry Acetyl-CoA carboxylase (ACCase) inhibitor. Rice/Echinochloa selectivity is mainly due to differential sensitivity to ACCase, and may also be due to differential foliar uptake. The (S)- isomer is less active than the (R)- isomer. Mode of action Causes chlorosis in developing leaves, with growth inhibition. Uses Post-emergence control of annual and perennial grass weeds (including Echinochloa spp., Leptochloa chinensis, Digitaria spp. and Eleusine indica) in various crops, including rice; applied at 90–200 g/ha for upland crops (wheat, soya beans, cotton, turf, etc.). Formulation types EC; GR; ME; WG . PRODUCTS: Other products ‘Pizero’ (Dongbu HiTek). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Never notifed and authorised in the EU. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >2000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Not a skin irritant; slightly irritating to eyes. May cause sensitisation by skin contact. Inhalation LC 50 (4 h) for rats >2.61 mg/l. Other Non-mutagenic in the Ames, chromosome aberration, cell mutation and micronucleus tests. ECOTOXICOLOGY: Fish LC 50 (96 h) for rainbow trout 0.307 mg/l. Daphnia EC 50 (48 h) 0.288 mg/l. Algae EC 50 (48 h) >2.03 mg/l. Bees LD 50 (contact and oral) >100 μg/bee. Worms LC 50 for earthworms >1000 ppm. ENVIRONMENTAL FATE: Soil/Environment Soil degradation is both chemical and microbial; DT 50 40–60 d (25 °C). Aqueous photolysis produces seven detectable metabolites; DT 50 18–120 d, depending on conditions. 362 The Pesticide Manual Sixteenth Edition © BCPC 2012 metfurazon metazoxolon Fungicide NOMENCLATURE: Common name metazoxolon (BSI, E-ISO, (m) F-ISO) IUPAC name 4-(3-chlorophenylhydrazono)-3-methyl-1,2-oxazol-5(4H)-one; 4-(3-chlorophenylhydrazono)-3-methylisoxazol-5(4H)-one Chemical Abstracts name 3-methyl-4,5-isoxazoledione 4-[(3-chlorophenyl)hydrazone] CAS RN [5707–73–3] Development codes PP395 Smiles code CC1=NOC(=O)C1=NNc2cccc(Cl)c2 PHYSICAL CHEMISTRY: Mol. wt. 237.6 M.f. C 10 H 8 ClN 3 O 2 COMMERCIALISATION: History Fungicide reported by T. J. Purnell (Proc. Br. Crop Prot. Conf., 7th, 1973, 2, 603). Evaluated by ICI Agrochemicals. APPLICATIONS: Uses Control of Pythium spp. on ornamentals, peanuts and peas, Rhizoctonia solani on cotton, Phytophthora capsici on peppers, Fusarium nivale on rye, and Fusarium nivale on wheat, when applied as a seed or soil treatment. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for female rats 3340 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg Not a skin or eye irritant. metfurazon Herbicide NOMENCLATURE: Common name metfurazon (BSI (from 1984), E-ISO); metfurazone (BSI (before 1984), (f) F-ISO) IUPAC name 4-chloro-5-dimethylamino-2-(α,α,α-trifuoro-m-tolyl)pyridazin-3(2H)-one Chemical Abstracts name 4-chloro-5-(dimethylamino)-2-[(3-trifuoromethyl) phenyl]-3(2H)-pyridazinone CAS RN [23576–23–0] Development codes SAN 6706H Smiles code CN(C)c1cnn(c2cccc(c2)C(F)(F)F)c(=O)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 317.7 M.f. C 13 H 11 ClF 3 N 3 O COMMERCIALISATION: History Herbicide evaluated by Sandoz AG. Supplementary Entries – Extended methacrifos 363 methacrifos Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name methacrifos (BSI, E-ISO, (m) F-ISO) IUPAC name methyl (E)-3-(dimethoxyphosphinothioyloxy)-2-methacrylate; (E)-O-2- methoxycarbonylprop-1-enyl O,O-dimethyl phosphorothioate Chemical Abstracts name (E)-methyl 3-[(dimethoxyphosphinothioyl)oxy]-2-methyl-2- propenoate CAS RN [62610–77–9] (E)- isomer; [30864–28–9] unstated stereochemistry EC no 250–366–2 Development codes CGA 20 168 Smiles code COC(=O) C(=COP(=S)(OC)OC)C PHYSICAL CHEMISTRY: Mol. wt. 240.2 M.f. C 7 H 13 O 5 PS Form Colourless liquid. B.p. 90 °C /0.01 mmHg V.p. 160 mPa (20 °C) K ow logP ≥3.0 Henry 9.61 × 10-2 Pa m 3 mol –1 (calc.) S.g./density 1.225 (20 °C) Solubility In water 400 mg/l (20 °C). Miscible with many organic solvents, e.g. methanol, benzene, hexane, and dichloromethane. Stability Relatively unstable in alkaline conditions; on hydrolysis DT 50 (calc.) (20 °C) 66 d (pH 1), 29 d (pH 7), 9.5 d (pH 9). Decomposes atc. 200 °C. F.p. 69–73 °C COMMERCIALISATION: History Insecticide reported by R. Wyniger et al. (Proc. Br. Crop Prot. Conf. - Pests Dis., 1977, 3, 1033). Introduced by Ciba-Geigy AG (later Novartis Crop Protection AG). Patents BE 766000; GB 1342630 Manufacturers Novartis APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Insecticide and acaricide with respiratory, contact, and stomach action. Gives rapid knockdown, and has long residual activity. Uses Mainly used for control of arthropod pests in stored products by incorporation or by surface treatment. Phytotoxicity Should not be used on plant foliage. Formulation types DP; EC. Compatibility Incompatible with strongly acidic or alkaline materials. PRODUCTS: Discontinued products ‘Damfn’* (Novartis). ANALYSIS: Product analysis by glc. Residues in grain determined by glc with FPD or TID (J. Desmarchelier et al., Pestic. Sci., 1977, 8, 473). O P(OCH 3 ) 2 S C C CH 3 H C O CH 3 O 364 The Pesticide Manual Sixteenth Edition © BCPC 2012 methanesulfonyl fuoride TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. JMPR Mtg. 65 (1992); JMPR Evaln. I 66 (1992); JMPR Evaln. II 61 (1990). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 678 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3100 mg/kg. Mild skin irritant; non-irritating to eyes (rabbits). Inhalation LC 50 (6 h) for rats 2.2 mg/l air. NOEL (2 y) for rats 0.6 mg/kg b.w. daily. ADI/RfD (JMPR) 0.006 mg/kg b.w. [1990]. Toxicity Class WHO (a.i.) II EC Classifcation Xn; R22| R43| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for Japanese quail 116 mg/kg. Fish LC 50 (96 h) for carp 30.0, rainbow trout 0.4 mg/l. ENVIRONMENTAL FATE: Animals Rapid excretion; metabolism via hydrolysis of the methyl esters as well as cleavage of the phosphoric and vinyl ester bonds, followed by mineralisation to CO 2 . methalpropalin Herbicide NOMENCLATURE: Common name methalpropalin (BSI, E-ISO); mé(thalpropaline) ((f) F-ISO) IUPAC name α,α,α-trifuoro-N-(2-methylallyl)-2,6-dinitro-N-propyl-p-toluidine Chemical Abstracts name N-(2-methyl-2-propenyl)-2,6-dinitro-N-propyl-4- (trifuoromethyl)benzenamine CAS RN [57801–46–4] Smiles code CCCN(CC(=C)C)c1c(cc(cc1[N+](=O)[O-])C(F)(F)F)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 347.3 M.f. C 14 H 16 F 3 N 3 O 4 COMMERCIALISATION: History Herbicide evaluated by Eli Lilly & Co. methanesulfonyl fuoride Insecticide NOMENCLATURE: IUPAC name methanesulfonyl fuoride (I) Chemical Abstracts name (I) Other names MSF CAS RN [558–25–8] Smiles code CS(=O)(=O)F PHYSICAL CHEMISTRY: Mol. wt. 98.10 M.f. CH 3 FO 2 S COMMERCIALISATION: History Fumigant insecticide marketed by Bayer AG. Supplementary Entries – Extended methasulfocarb 365 APPLICATIONS: Mode of action Fumigant insecticide. PRODUCTS: Discontinued products ‘Fumette’* (Bayer). methasulfocarb Fungicide, plant growth regulator FRAC 42, U; thiocarbamate fungicide NOMENCLATURE: Common name mé(thasulfocarb) ((m) F-ISO); methasulfocarb (BSI, E-ISO) IUPAC name S-4-methylsulfonyloxyphenyl methylthiocarbamate Chemical Abstracts name S-[4-[(methylsulfonyl)oxy]phenyl] methylcarbamothioate CAS RN [66952–49–6] Development codes NK-191 (Nippon Kayaku) Smiles code CNC(=O)Sc1ccc(OS(=O)(=O)C)cc1 PHYSICAL CHEMISTRY: Mol. wt. 261.3 M.f. C 9 H 11 NO 4 S 2 Form Colourless crystals. M.p. 137.5–138.5 °C Solubility In water 480 mg/l. Soluble in acetone, alcohols, and benzene. Stability Stable to light. COMMERCIALISATION: History Fungicide and plant growth regulator reported by K. Ohmori (Jpn. Pestic. Inf., 1985, No. 46, p. 17). Introduced in Japan (1984) by Nippon Kayaku Co., Ltd. Patents US 4126696; DE 2745229; JP 5347527 Manufacturers Nippon Kayaku APPLICATIONS: Uses Soil fungicide for control of Corticium, Fusarium, Mucor, Pseudomonas, Pythium, Rhizopus, Rhizoctonia, and Trichoderma spp. in rice. Application rate 0.6–1 g/rice nursery tray. Formulation types DP . PRODUCTS: Discontinued products ‘Kayabest’* (Nippon Kayaku). ANALYSIS: Product and residue analysis by glc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 112–119, male mice 342, female mice 262 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and mice >5000 mg/kg. Inhalation LC 50 (4 h) for rats >0.44 mg/l air. Other Non-mutagenic to mice. Non-teratogenic to rats. Toxicity Class WHO (a.i.) II ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 1.95 mg/l. CH 3 NHCOS OSO 2 CH 3 366 The Pesticide Manual Sixteenth Edition © BCPC 2012 methazole methazole Herbicide NOMENCLATURE: Common name methazole (BSI, ANSI, Australia, WSSA) IUPAC name 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione Chemical Abstracts name 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine- 3,5-dione CAS RN [20354–26–1] EC no 243–761–6 Development codes VCS-438 (Sandoz) Smiles code Cn1c(=O)on(c2ccc(Cl)c(Cl)c2)c1=O PHYSICAL CHEMISTRY: Composition Tech. is 95%. Mol. wt. 261.1 M.f. C 9 H 6 Cl 2 N 2 O 3 Form Colourless crystals; (tech. a light tan solid). M.p. 123–124 °C V.p. 0.133 mPa (25 °C) K ow logP = 2.59±0.04 (25 °C) Henry 2.32 × 10-2 Pa m 3 mol –1 (calc.) S.g./density 1.24 (25 °C) Solubility In water 1.5 mg/l (25 °C). In DMF 323, dichloromethane 255, cyclohexanone 171, acetone 40, xylene 55, methanol 6.5 (all in g/l, 25 °C). Stability Solutions in methanol undergo photodecomposition when exposed to uv light. Suspensions in water, when exposed to sunlight, are more stable (G. W. Ivie et al., J. Agric. Food Chem., 1973, 21, 386). Hydrolysed in strongly acidic and alkaline media. Decomposes below the b.p. COMMERCIALISATION: History Herbicide reported by W. Furness (Proc. Int. Congr. Plant Prot., 7th, Paris, 1970, p. 314). Introduced by Velsicol Chemical Corp. and later manufactured and marketed by Sandoz AG. Patents US 3437664 APPLICATIONS: Mode of action Selective systemic herbicide, absorbed by the roots and leaves, with translocation. Uses Used to control certain grasses and many broad-leaved weeds: pre- emergence in garlic and potatoes (1–2 kg/ha); as a directed spray on to soil or emerged weeds in citrus, stone-fruit, nuts, tea and established vines (6 kg/ha) and on cotton 15 cm tall (1–2 kg/ha), onions (>2 leaves) (2.5 kg/ha), newly seeded or winter-dormant alfalfa (>1 y old) (2.25 kg/ha). Preferably applied to moist soil; lower rates were applicable to light sandy soils. Formulation types WP; GR; WG . Compatibility Incompatible with some ester-type hormone herbicides. PRODUCTS: Discontinued products ‘Probe’* (Sandoz); ‘Tunic’* (Sandoz). ANALYSIS: Product analysis by lc and i.r. spectrophotometry (AOAC Methods, 18th Ed., 992.02, 982.03; N O N Cl Cl CH 3 O O Supplementary Entries – Extended methfuroxam 367 D. M. Whiteacre et al., Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 367). Residues determined by glc with ECD (idem, ibid.) or by hplc (idem, ibid.). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2500 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >12 500 mg/kg. Mild irritant to skin and eyes (rabbits). No skin sensitisation (guinea pigs). Chloracne observed in rabbit-ear studies and among certain workers at manufacturing plants. Inhalation LC 50 (4 h) for rats >200 mg/l air (dust). NOEL In 2-year feeding trials in rats and mice, a yellow-brown pigment occurred in the spleen or liver at >100 mg/kg diet. Non-mutagenic and non-teratogenic in rabbits (at up to 60 mg/kg daily), but foetal toxicity observed at ≥30 mg/kg daily. In a 3-generation study in rats, NOEL was 50 mg/kg diet (cataracts were observed at ≥100 mg/kg diet, but no other ill-effects). Toxicity Class WHO (a.i.) III EC Classifcation Xn; R21/22| Xi; R36/38| N; R51, R53 ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks 11 200, bobwhite quail 1825 mg/kg diet. In 1-generation study NOEL for bobwhite quail and mallard ducks 3 mg/kg diet. Fish LC 50 (96 h) for bluegill sunfsh 4.47, rainbow trout 4.09 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Plants In plants, methazole undergoes decarboxylation to 1-(3,4-dichlorophenyl)-3- methylurea, which is further degraded by N-demethylation to 3,4-dichlorophenylurea, and then to 3,4-dichloroaniline. Degradation is almost complete within 3 d. Soil/Environment Microbially degraded in soil by the same route as in plants. Soil DT 50 <30 d. methfuroxam Fungicide NOMENCLATURE: Common name methfuroxam (BSI, E-ISO, ANSI); mé(thfuroxame) ((m) F-ISO) IUPAC name 2,4,5-trimethyl-3-furanilide Chemical Abstracts name 2,4,5-trimethyl-N-phenyl-3-furancarboxamide CAS RN [28730–17–8] Development codes H719 (Uniroyal) Smiles code Cc1oc(C)c(C(=O)Nc2ccccc2)c1C PHYSICAL CHEMISTRY: Mol. wt. 229.3 M.f. C 14 H 15 NO 2 Form Colourless crystals with a faint odour. M.p. 138–142 °C V.p. <13 Pa (20 °C) Solubility In water 10 mg/l (25 °C). In DMF 412, acetone 125, methanol 64, benzene 36 (all in g/kg). Stability Hydrolysed by strong acids and alkalis. 368 The Pesticide Manual Sixteenth Edition © BCPC 2012 methiobencarb COMMERCIALISATION: History Fungicide reported by K. T. Alcock (Plant Dis. Reptr., 1978, 62, 854). Introduced in Germany by Uniroyal Chemical Co., Inc. Patents DE 2006471 APPLICATIONS: Biochemistry Inhibitor of succinate dehydrogenase complex, in the respiratory electron transport chain. Mode of action Systemic fungicide. Uses Seed treatment for control of Tilletia and Ustilago spp. in cereals applied at up to 50 g/100 kg seed. Formulation types DS; FS; LS; WS . PRODUCTS: Discontinued products ‘Trivax’* (Uniroyal). ANALYSIS: Product analysis by gc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 4300, female rats 1470, mice 620–880, dogs 10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 3160 mg/kg. No skin irritation (rabbits); slight irritation of mucous membranes. Inhalation LC 50 for rats 17.39 mg/l air. NOEL In 90 d feeding trials, no ill-effects were observed in rats at 300 mg/kg diet or in dogs at 1000 mg/kg diet. ECOTOXICOLOGY: Fish LC 50 for bluegill sunfsh 0.18, rainbow trout 0.26 mg/l. Bees Combinations with imazalil and thiabendazole are not hazardous to bees when used as recommended. ENVIRONMENTAL FATE: Plants After application of 30 g methfuroxam per 100 kg seed, the residue levels in unripe and ripe maize are 0.02–0.13 and 0–0.01 mg/kg, respectively. methiobencarb Herbicide NOMENCLATURE: Common name methiobencarb (BSI, E-ISO); mé(thiobencarbe) ((m) F-ISO) IUPAC name S-4-methoxybenzyl diethylthiocarbamate Chemical Abstracts name S-[(4-methoxyphenyl)methyl] diethylcarbamothioate CAS RN [18357–78–3] Development codes NTN 5810 Smiles code CCN(CC)C(=O)SCc1ccc(OC)cc1 PHYSICAL CHEMISTRY: Mol. wt. 253.4 M.f. C 13 H 19 NO 2 S COMMERCIALISATION: History Herbicide evaluated by Bayer AG. Supplementary Entries – Extended methocrotophos 369 methiuron Herbicide NOMENCLATURE: Common name methiuron (BSI, E-ISO, (m) F-ISO) IUPAC name 1,1-dimethyl-3-m-tolyl-2-thiourea Chemical Abstracts name N,N-dimethyl-N′-(3-methylphenyl)thiourea CAS RN [21540–35–2] Development codes MH 090 Smiles code CN(C)C(=S)Nc1cccc(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 194.3 M.f. C 10 H 14 N 2 S Form Colourless crystals. M.p. 145 °C Solubility In water 400 mg/l (25 °C). In methanol 70, pyridine 470 (both g/l, 25 °C). Stability Hydrolysed by concentrated acids; stable to light. COMMERCIALISATION: History Herbicide introduced by Yorkshire Tar Distillers Ltd. APPLICATIONS: Mode of action Selective herbicide. Uses Used at 1.12–2.24 kg/ha for selective pre-em. control of weeds in onions, potatoes and sugar beet, and at 2.24 kg/ha post-em. in brassicas and onions when the weeds are at the seedling stage. Formulation types EC; GR . ANALYSIS: Product analysis is by hydrolysis with acid, distillation of the m-toluidine released which is measured by titration. Residues may be determined by colorimetry of a derivative of m-toluidine, which has been formed by hydrolysis. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for ratsc. 2200 mg/kg. Toxicity Class WHO (a.i.) O ENVIRONMENTAL FATE: Soil/Environment Persists in soilc. 50 d at 15 °C. methocrotophos Insecticide IRAC 1B NOMENCLATURE: Common name methocrotophos (BSI, E-ISO); mé(tocrotophos) ((m) F-ISO) IUPAC name (E)-2-(N-methoxy-N-methylcarbamoyl)-1-methylvinyl dimethyl phosphate; 3-dimethoxyphosphinoyloxy-N-methoxy-N-methylisocrotonamide Chemical Abstracts name (E)-3-(methoxymethylamino)-1-methyl-3-oxo-1- propenyl dimethyl phosphate CAS RN [25601–84–7] Development codes C 2307 Smiles code COCNC(=O)C=C(C)OP(=O)(OC)OC PHYSICAL CHEMISTRY: Mol. wt. 253.2 M.f. C 8 H 16 NO 6 P 370 The Pesticide Manual Sixteenth Edition © BCPC 2012 methoprotryne COMMERCIALISATION: History Insecticide evaluated by Ciba AG (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. methometon Herbicide NOMENCLATURE: Common name methometon (BSI, E-ISO); mé(tomé) ((m) F-ISO) IUPAC name 6-methoxy-N 2 ,N4-bis(3-methoxypropyl)-1,3,5-triazine-2,4-diamine Chemical Abstracts name 6-methoxy-N,N′-bis(3-methoxypropyl)-1,3,5- triazine-2,4-diamine CAS RN [1771–07–9] Development codes G 34 690 Smiles code COCCCNc1nc(NCCCOC)nc(OC)n1 PHYSICAL CHEMISTRY: Mol. wt. 285.3 M.f. C 12 H 23 N 5 O 3 COMMERCIALISATION: History Herbicide evaluated by J. R. Geigy S.A. (later Ciba-Geigy AG). methoprotryne Herbicide NOMENCLATURE: Common name methoprotryn (WSSA); methoprotryne (BSI, E-ISO); mé(toprotryne) ((f) F-ISO) IUPAC name N 2 -isopropyl-N4-(3-methoxypropyl)-6-methylthio-1,3,5-triazine-2,4- diamine Chemical Abstracts name N-(3-methoxypropyl)-N′-(1-methylethyl)-6-(methylthio)- 1,3,5-triazine-2,4-diamine CAS RN [841–06–5] Development codes G 36 393 Smiles code COCCCNc1nc(NC(C)C)nc(SC)n1 PHYSICAL CHEMISTRY: Mol. wt. 271.4 M.f. C 11 H 21 N 5 OS Form Colourless powder. M.p. 68–70 °C V.p. 0.038 mPa (20 °C) Henry 3.22 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.186 (20 °C) Solubility In water 320 mg/l (20 °C). In acetone 450, dichloromethane 650, hexane 5, methanol 400, octanol 150, toluene 380 (all in g/l, 20 °C). Stability Hydrolysed N N N NH(CH 2 ) 3 OCH 3 CH 3 S NHCH(CH 3 ) 2 Supplementary Entries – Extended methoprotryne 371 in aqueous alkaline and acidic media to the inactive 2-hydroxytriazine. pKa Basic, 4.0 (21 °C) COMMERCIALISATION: History Herbicide reported by A. Gast et al. (Z. Pfanzenkr. Pfanzenpathol. Pfanzenschutz, 1965, 72, 325). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). Patents BE 584306; GB 927348 APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective herbicide, absorbed by the leaves and roots. Uses Selective post-emergence control of annual broad-leaved weeds and grasses in winter-sown cereals at 1.5–2.0 kg/ha. Formulation types WP. PRODUCTS: Discontinued products ‘Gesaran’* (Ciba-Geigy). ANALYSIS: Product analysis by glc (CIPAC Handbook, 1983, 1B, 1864; 1980, 1A, 1302). Residues determined by glc (K. Ramsteiner et al., J. Assoc. Off. Anal. Chem., 1974, 57, 192). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000, mice 2400 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >150 mg/kg. Not a skin irritant (rats). NOEL (90 d) for rats 3750 mg a.i./kg diet (c 250 mg a.i./kg daily); for dogs 11 250 mg/kg diet (c. 375 mg/kg daily). Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Fish LC 50 (96 h) for bluegill sunfsh 9.8, rainbow trout 8, and crucian carp 31 mg/l. Bees Non-toxic to bees. ENVIRONMENTAL FATE: Plants In plants, the thiomethyl group is replaced by hydroxyl, presumably after oxidation of the sulfur to sulfoxide and sulfone. Demethylation of the amino groups at C4 and C6 occurs, with cleavage of the amine moieties and their replacement by hydroxyl, presumably followed by ring opening. Soil/Environment In soil, the thiomethyl group is replaced by hydroxyl, presumably after oxidation of the sulfur to sulfoxide and sulfone. Demethylation of the amino groups at C4 and C6 occurs, with cleavage of the amine moieties and their replacement by hydroxyl, presumably followed by ring opening. 372 The Pesticide Manual Sixteenth Edition © BCPC 2012 methoxychlor methoquin-butyl Insecticide NOMENCLATURE: Common name mé(thoquine-butyl) ((m) F-ISO); methoquin-butyl (BSI, E-ISO) IUPAC name butyl 3-methylquinoline-4-carboxylate Chemical Abstracts name butyl 3-methyl-4-quinolinecarboxylate Other names BMC CAS RN [19764–43–3] Smiles code CCCCOC(=O)c1c(C)cnc2ccccc12 PHYSICAL CHEMISTRY: Mol. wt. 243.3 M.f. C 15 H 17 NO 2 COMMERCIALISATION: History Insecticide. methoxychlor Insecticide IRAC 3B NOMENCLATURE: Common name methoxychlor (BSI, E-ISO, ESA, JMAF); mé(thoxychlore) ((m) F-ISO) IUPAC name 1,1,1-trichloro-2,2-bis(4-methoxyphenyl)ethane Chemical Abstracts name 1,1′-(2,2,2-trichloroethylidene)bis[4-methoxybenzene] Other names DMDT CAS RN [72–43–5] Offcial codes OMS 466; ENT 1716 Smiles code COc1ccc(cc1)C(c2ccc(OC)cc2)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Composition Tech. grade contains ≥88% methoxychlor and ≤12% related isomers. Mol. wt. 345.7 M.f. C 16 H 15 Cl 3 O 2 Form Colourless crystals; (tech., grey powder). M.p. 89 °C; (tech., 77 °C) V.p. Very low S.g./density 1.41 (25 °C) Solubility In water 0.1 mg/l (25 °C). Readily soluble in aromatic, chlorinated and ketonic solvents, and vegetable oils. In chloroform and xylene 440, methanol 50 (all in g/kg, 22 °C). Stability Stable to oxidising agents and to uv irradiation. Reacts with alkalis, especially in the presence of catalytically-active metals, with loss of hydrogen chloride, but more slowly than DDT. Colour turns to pink or tan on exposure to light. COMMERCIALISATION: History Insecticide reported by P. Läuger et al. (Helv. Chim. Acta, 1944, 27, 892). Introduced by J. R. Geigy AG (now Syngenta AG) and by E. I. du Pont de Nemours & Co. (neither company now manufactures or markets it). Patents CH 226180; GB 547871 (to Ciba- Geigy); US 2420928; US 2477655; GB 624561 (to DuPont) CH 3 O CH CCl 3 OCH 3 Supplementary Entries – Extended methoxychlor 373 APPLICATIONS: Biochemistry Acts on the nervous system of insects and disturbs the function of neurons by interaction with the sodium channel. Mode of action Insecticide with contact and stomach action. Uses Control of a wide range of insect pests (particularly chewing insects) in feld crops, forage crops, fruit, vines, fowers, vegetables, and in forestry. Used also for control of insect pests in animal houses, dairies, and in household and industrial premises. Formulation types AE; DP; EC; GR; WP. Compatibility Incompatible with highly alkaline materials. PRODUCTS: Discontinued products ‘Marlate’* (Kincaid); ‘Sixanol’* (Quinta). ANALYSIS: Product analysis by total chlorine content (H. L. Pease, J. Assoc. Off. Anal. Chem., 1976, 58, 40). Residues determined by glc, tlc or paper chromatography (AOAC Methods, 18th Ed., 970.52; J. Solomon & W. L. Lockhart, J. Assoc. Off. Anal. Chem., 1978, 60, 690; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 441) or colorimetrically (AOAC Methods, 18th Ed., 954.09; ibid. 10th Ed., 24.148–24.152). See also Pestic. Anal. Man., I, 208, 303, 304, 502; ibid., II, 180.120. In drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 29 (1977). PDS 28 (1977). ICSC.306 (1999). IARC 20 (1979). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for rats 6000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Not a skin irritant. NOEL In 1 y feeding trials, no toxic effect observed in dogs receiving 300 mg/kg daily; in 2 y trials in rats, no effect at 200 mg/kg diet, but some reduction in growth occurred at 1600 mg/kg diet. ADI/RfD (JMPR) 0.1 mg/kg b.w. [1977]; (EPA) cRfD 0.005 mg/kg b.w. [1991]. Water GV 0.02 mg/l Toxicity Class WHO (a.i.) U. ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks >2000 mg/kg. Dietary LC 50 (8 d) for bobwhite quail and ring-necked pheasants >5000 mg/kg diet. Fish LC 50 (24 h) for rainbow trout 0.052, bluegill sunfsh 0.067 mg/l. Daphnia LC 50 (48 h) 0.00078 mg/l. ENVIRONMENTAL FATE: Animals Degradation in animals is principally by O-dealkylation to the corresponding phenol and diphenol, and by dehydrochlorination to 4,4′-dihydroxybenzophenone (K. S. Kapoor, J. Agric. Food Chem., 1970, 18, 1145–1152; J. Pestic. Sci., 1989, 14, 85; M. D. Corbett et al., Chem. Res. Toxicol., 1990, 3, 8). Soil/Environment DT 50 in waterc. 46 d. 374 The Pesticide Manual Sixteenth Edition © BCPC 2012 2-methoxyethylmercury silicate 2-methoxyethylmercury acetate Fungicide NOMENCLATURE: IUPAC name 2-methoxyethylmercury acetate Chemical Abstracts name (acetato-O)(2-methoxyethyl)mercury CAS RN [151–38–2] EC no 205–790–2 Smiles code COCC[Hg]OC(=O)C PHYSICAL CHEMISTRY: Mol. wt. 318.7 M.f. C 5 H 10 HgO 3 COMMERCIALISATION: History Fungicide introduced by Kenogard VT AB. APPLICATIONS: Uses A fungicide used to protect seeds of cereals, cotton, fax, oilseed rape and sugar beet from infection by Alternaria, Botrytis, Drechslera, Fusarium, Phoma, Pythium, Rhizoctonia, Septoria and Tilletia spp. and Ustilago hordei. Formulation types LS . PRODUCTS: Discontinued products ‘Panogen’* (Kenogard AB). ANALYSIS: Product analysis by titration (AOAC Methods, 18th Ed., 971.04) or gravimetrically (ibid., 973.11). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 1 (1976), 86 (1989), both general reviews of mercury and its compounds. JMPR Evaln. 9 (1967) EU Status (1107/2009) Alkoxyalkyl mercury compounds considered to be outside the scope of the Directive; already banned, 79/117/EEC. MAMMALIAN TOXICOLOGY: IARC Class Methylmercury compounds are classifed 2B EC Classifcation Not specifed, but organic mercury generally is assigned T+; R26/27/28| R33| N; R50, R53, concentration-dependent. PIC Not specifcally listed in the relevant DGD, but all mercury compounds are included in the PIC procedure. 2-methoxyethylmercury silicate Fungicide NOMENCLATURE: IUPAC name The compound is an organomercury silicate but there is some doubt about whether it is an orthosilicate or a metasilicate and therefore about its true molecular structure Chemical Abstracts name hydrogen [metasilicato(2–)-O](2-methoxyethyl) mercurate(1–) CAS RN [64491–92–5] PHYSICAL CHEMISTRY: Form Colourless crystalline powder. V.p. 440 mPa (35 °C) Solubility Practically insoluble Supplementary Entries – Extended methoxyphenone 375 in water. Stability 2-Methoxyethylmercury salts are stable to alkali but are decomposed by halogen acids (J. Chatt, Chem. Rev. 1951 48, 7). COMMERCIALISATION: History Fungicide introduced by I. G. Farbenindustrie AG (later Bayer AG). APPLICATIONS: Uses In seed treatments, against various seed-borne diseases of cereals. Formulation types DS . PRODUCTS: Discontinued products ‘Ceresan Universal Dry Seed Treatment’* (Bayer); ‘Soprasan’* (Sopra). ANALYSIS: Product analysis by titration (CIPAC Handbook, 1970, 1, 503; AOAC Methods, 18th Ed., 971.04) or gravimetry (ibid., 973.11). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 9 (1967) MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1140 mg formulated product/kg. Toxicity Class WHO (a.i.) IIIPIC Not specifcally listed in the relevant DGD, but all mercury compounds are included in the PIC procedure. methoxyphenone Herbicide NOMENCLATURE: Common name methoxyphenone (JMAF) IUPAC name 4-methoxy-3,3′-dimethylbenzophenone Chemical Abstracts name (4-methoxy-3-methylphenyl)(3-methylphenyl) methanone CAS RN [41295–28–7] Development codes NK-049 (Nippon Kayaku) Smiles code COc1ccc(cc1C)C(=O)c2cccc(C)c2 PHYSICAL CHEMISTRY: Mol. wt. 240.3 M.f. C 16 H 16 O 2 Form Colourless crystals. M.p. 62.0–62.5 °C Solubility In water 2 mg/l (20 °C). Soluble in most organic solvents. Stability Stable under acid and alkaline conditions, but slowly decomposed by sunlight. COMMERCIALISATION: History Herbicide reported (Proc. Asian-Pacifc Weed Sci. Soc. Conf., 4th, 1973, p. 215). Introduced by Nippon Kayaku Co., Ltd. Patents JP 51005446; GB 1355926; US 3873304 APPLICATIONS: Biochemistry Inhibits photosynthesis. Mode of action Selective herbicide, inducing chlorosis. Uses A selective pre-em. herbicide effective against annual grasses and broad- leaved weeds in paddy rice and vegetable crops at 3–5 kg/ha; also used in rice pre-em. in 376 The Pesticide Manual Sixteenth Edition © BCPC 2012 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate combination with bensulide, at 30–50 kg granules/ha. Formulation types WP. PRODUCTS: Discontinued products ‘Kayametone’* (Nippon Kayaku). ANALYSIS: Product and residue analysis by glc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >4000 mg/kg. NOEL (90 d) for rats 1500 mg/kg diet, for mice 1000 mg/kg diet. Toxicity Class WHO (a.i.) U ENVIRONMENTAL FATE: Soil/Environment It is biodegradable, leaving no residue problems. 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate Insecticide NOMENCLATURE: IUPAC name 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate Chemical Abstracts name 3,5-dimethyl-4-(methyl-2-propynylamino)phenyl methylcarbamate CAS RN [23623–49–6] Development codes C 20 132 Smiles code CNC(=O)Oc1cc(C)c(N(C)CC#C)c(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 246.3 M.f. C 14 H 18 N 2 O 2 COMMERCIALISATION: History Insecticide evaluated by Ciba AG (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact and ingested insecticide. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 30 mg/kg. 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate Insecticide NOMENCLATURE: IUPAC name 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate Chemical Abstracts name 2-(methyl-2-propynylamino)phenyl methylcarbamate CAS RN [23504–07–6] Development codes C 17 018 Smiles code CNC(=O)Oc1ccccc1N(C)CC#C PHYSICAL CHEMISTRY: Mol. wt. 218.3 M.f. C 12 H 14 N 2 O 2 Supplementary Entries – Extended methylarsenic sulfde 377 COMMERCIALISATION: History Insecticide evaluated by Ciba AG (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Contact insecticide. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 60 mg/kg. 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid Fungicide, herbicide, nematicide NOMENCLATURE: IUPAC name 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid; tetrahydro-5-methyl-6- thioxo-2H-1,3,5-thiadiazin-3-ylacetic acid Chemical Abstracts name dihydro-5-methyl-6-thioxo-2H-1,3,5-thiadiazine- 3(4H)-acetic acid Other names thiadiazinthion CAS RN [3655–88–7] Smiles code CN1CN(CC(=O)O)CSC1=S PHYSICAL CHEMISTRY: Mol. wt. 206.3 M.f. C 6 H 10 N 2 O 2 S 2 COMMERCIALISATION: History Nematicide introduced by Bayer AG. PRODUCTS: Discontinued products ‘Terracur’* (Bayer). methylarsenic sulfde Fungicide NOMENCLATURE: IUPAC name methylarsenic sulfde Chemical Abstracts name methylthioxoarsine Other names MAS CAS RN [2533–82–6] Smiles code C[As]=S PHYSICAL CHEMISTRY: Mol. wt. 122.0 M.f. CH 3 AsS Form Colourless fakes with an unpleasant odour. M.p. 110 °C Solubility Practically insoluble in water. Readily soluble in carbon disulfde; less soluble in chlorinated hydrocarbons, DMF, diethyl ether, ethanol, pyridine. COMMERCIALISATION: History Fungicidal properties of this chemical, which was reported in 1858 (von Bayer, Ann. Chem. Pharm., 1858, 107, 279), described in 1931. Introduced by Bayer AG (1958). Patents DE 1079886 APPLICATIONS: Uses Used as a seed or soil treatment to control Rhizoctonia solani and other soil fungi. 378 The Pesticide Manual Sixteenth Edition © BCPC 2012 methyldymron PRODUCTS: Discontinued products ‘Rhizoctol’* (Bayer); ‘Urbasulf ’* (Bayer); Discontinued mixtures ‘Rhizoctol combi’* (+ benquinox) (Bayer); ‘Rhizoctol slurry’* (+ benquinox) (Bayer). ANALYSIS: Product analysis is by conversion to arsine which was measured by titration with bromine. Residues may be determined by a colorimetric method after conversion to arsenate (H. Frehse & H.Tietz, J. Agric. Food Chem., 1959, 7, 553). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: Arsenic and arsenic compounds are reviewed in EHC 224 (2001). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 100 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 1400 mg/kg. Skin irritation occurred to 6 persons after a 4-h exposure of a moistened formulation (equivalent to 48 g arsenic/kg). EC Classifcation Not specifed, but arsenic compounds in general (with exceptions) are assigned T; R23/25| N; R50, R53| concn. dep. methyldymron Herbicide HRAC Z NOMENCLATURE: Common name methyldymron (JMAF) IUPAC name 1-methyl-3-(1-methyl-1-phenylethyl)-1-phenylurea; 3-(α,α-dimethylbenzyl)- 1-methyl-1-phenylurea Chemical Abstracts name N-methyl-N′-(1-methyl-1-phenylethyl)-N-phenylurea CAS RN [42609–73–4] Development codes K-1441; SK-41 (SDS Biotech KK) Smiles code CN(C(=O)NC(C)(C)c1ccccc1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 268.4 M.f. C 17 H 20 N 2 O Form Colourless, odourless crystals. M.p. 72 °C K ow logP = 3.01 S.g./density 1.1–1.2 Solubility In water 120 mg/l (20 °C). In acetone 913, hexane 8.2, methanol 637 (all in g/l, 20 °C). Stability Stable to heat and uv light. COMMERCIALISATION: History Herbicide reported by T. Takematsu et al. (Proc. 5th Asian-Pacifc Weed Sci. Soc. Conf., 1975, 121). Introduced in Japan (1978) by Showa Denko (agrochemical interests later SDS Biotech K.K.). Patents JP 7242493 NHCON CH 3 C CH 3 CH 3 Supplementary Entries – Extended methyl isothiocyanate 379 APPLICATIONS: Biochemistry Cell division inhibitor. Mode of action Selective herbicide, absorbed principally by the roots, with translocation to the meristem. Uses Pre- and early post- emergence control of cyperaceous and some annual grass weeds in turf, at 2–10 kg/ha. Formulation types WP. PRODUCTS: Discontinued products ‘Stacker’* (SDS Biotech K.K.). ANALYSIS: Product and residue analysis by glc and hplc; details available from SDS Biotech. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male mice 5000, female mice 5269, male rats 5852, female rats 3948 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Inhalation LC 50 (14 d) for rats >4.85 mg/l. NOEL (90 d) for male rats 26.4, female rats 25.6 mg/kg diet. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 14 mg/l. Daphnia LC 50 (3 h) for D. pulex >40 ppm. ENVIRONMENTAL FATE: Plants Rapidly metabolised in plants. methyl isothiocyanate Fungicide, herbicide, insecticide, nematicide NOMENCLATURE: Common name isothiocyanate de mé(thyle) (F-ISO, accepted in lieu of a common name); methyl isothiocyanate (BSI, E-ISO, JMAF, accepted in lieu of a common name) IUPAC name methyl isothiocyanate Chemical Abstracts name isothiocyanatomethane Other names MIT; MITC CAS RN [556–61–6] EC no 209–132–5 Smiles code CN=C=S PHYSICAL CHEMISTRY: Composition Tech. is ≥94.5% pure. Mol. wt. 73.1 M.f. C 2 H 3 NS Form Colourless crystals, with a horseradish-like odour. M.p. 35–36 °C; (tech., 25.3–27.6 °C) B.p. 118–119 °C V.p. 2.13 kPa (25 °C) K ow logP = 1.37 (calc.) S.g./density 1.069 (37 °C); (tech., 1.0537 (40 °C)) Solubility In water 8.2 g/l (20 °C). Readily soluble in common organic solvents, such as ethanol, methanol, acetone, cyclohexanone, dichloromethane, chloroform, carbon tetrachloride, benzene, xylene, petroleum ether and mineral oils. Stability Unstable and reactive. Rapidly hydrolysed by alkalis, more slowly in acidic and neutral solutions, DT 50 85 h (pH 5), 490 h (pH 7), 110 h (pH 9) (25 °C). Sensitive to oxygen and to light. Stable up to 200 °C. pKa 12.3 F.p. 26.9 °C CH 3 NCS 380 The Pesticide Manual Sixteenth Edition © BCPC 2012 methyl isothiocyanate COMMERCIALISATION: History Nematicidal activity reported by E. A. Pieroh et al. (Anz. Schädlingsskd., 1959, 32, 183). Introduced by Schering AG (now Bayer AG). Patents US 3113908 Manufacturers Bayer CropScience APPLICATIONS: Uses Multi-purpose soil fumigant for control of nematodes, soil fungi, soil insects, and weed seeds. Phytotoxicity Phytotoxic to all green plants. Formulation types EC. PRODUCTS: Discontinued products ‘Trapex’* (Aventis); ‘Trapexide’* (Aventis). ANALYSIS: Product analysis by glc or by hplc. Residues determined by glc with FPD (M. Ottnad et al., Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 563). Details available from Bayer CropScience. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 72–220, mice 90–104 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 2780, male mice 1870, rabbits 263 mg/kg. Strongly irritating to eyes and skin (rabbits). Inhalation LC 50 (1 h) for rats 1.9 mg/l air. NOEL (2 y) for rats 10 mg/l drinking water (0.37–0.56 mg/kg b.w. daily); (2 y) for mice 20 mg/l drinking water (3.48 mg/kg b.w. daily); (1 y) for dogs 0.4 mg/kg b.w.. daily (by gavage). ADI/RfD (BfR) 0.004 mg/kg b.w. [2005]. Other Not carcinogenic. Toxicity Class WHO (a.i.) II. EC Classifcation T; R23/25| C; R34| R43| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks 136 mg/kg. Dietary LC 50 (5 d) for mallard ducks 10 936, pheasants >5000 mg/kg diet. Fish LC 50 (96 h) for bluegill sunfsh 0.14, rainbow trout 0.09, mirror carp 0.37–0.57 mg/l. Daphnia LC 50 (48 h) 0.055mg/l. Algae EC 50 (96 h) 0.248 mg/l; NOEC (96 h) 0.125 mg/l. Bees Not hazardous to bees when used as directed. ENVIRONMENTAL FATE: Soil/Environment In damp soil, degradation and evaporation of the bulk of the substance occurs within 3 weeks at 18–20 °C soil temperature, 4 weeks at 6–12 °C, and 8 weeks at 0–6 °C. At the lower temperatures, leaching is more signifcant and is dependent on soil moisture. The potential for groundwater contamination is small, due to low leaching and fast degradation. Supplementary Entries – Extended 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate 381 methylmercury dicyandiamide Fungicide NOMENCLATURE: Common name methylmercury dicyandiamide (BSI, accepted in lieu of a common name.) IUPAC name 1-cyano-3-(methylmercurio)guanidine; (methylmercurio) guanidinocarbonitrile Chemical Abstracts name (cyanoguanidinato-N′)methylmercury CAS RN [502–39–6] Smiles code C[Hg]NC(=N)NC#N PHYSICAL CHEMISTRY: Mol. wt. 298.7 M.f. C 3 H 6 HgN 4 COMMERCIALISATION: History Fungicide introduced in Sweden in 1938, and in USA by Panogen Inc. PRODUCTS: Discontinued products ‘Panogen’* (Panogen). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 9 (1967) EU Status (1107/2009) Alkyl mercury compounds considered to be outside the scope of the Directive; already banned, 79/117/EEC. MAMMALIAN TOXICOLOGY: IARC Class methylmercury compounds are classifed 2B. Toxicity Class WHO (a.i.) O EC Classifcation Not specifed, but organic mercury generally is assigned T+; R26/27/28| R33| N; R50, R53 (concentration-dependent). PIC Yes. 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate Insecticide NOMENCLATURE: IUPAC name 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate Chemical Abstracts name 3-methyl-1-phenyl-1H-pyrazol-5-yl dimethylcarbamate CAS RN [87–47–8] Development codes G 22 008 Smiles code CN(C)C(=O)Oc1cc(C)nn1c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 245.3 M.f. C 13 H 15 N 3 O 2 COMMERCIALISATION: History Insecticide introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Pyrolan’* (Ciba-Geigy). 382 The Pesticide Manual Sixteenth Edition © BCPC 2012 metobenzuron metobenzuron Herbicide NOMENCLATURE: Common name mé(tobenzuron) ((m) F-ISO); metobenzuron (BSI, E-ISO) IUPAC name (±)-1-methoxy-3-[4-(2-methoxy-2,4,4-trimethylchroman-7-yloxy)phenyl]-1- methylurea Chemical Abstracts name (±)-N′-[4-[(3,4-dihydro-2-methoxy-2,4,4-trimethyl-2H- 1-benzopyran-7-yl)oxy]phenyl]-N-methoxy-N-methylurea CAS RN [111578–32–6] Development codes UMP-488 (Mitsui Petrochemical) Smiles code CON(C)C(=O)Nc1ccc(Oc2ccc3c(OC(C)(CC3(C)C)OC)c2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 400.5 M.f. C 22 H 28 N 2 O 5 Form White powder. M.p. 101.0–102.5 °C Solubility In water 0.4 mg/l (25 °C). COMMERCIALISATION: History Reported by T. Morimoto et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1993, 1, 67). Introduced by Mitsui Petrochemical Industries Ltd (became Mitsui Chemicals Inc.). APPLICATIONS: Biochemistry Inhibitor of photosynthesis. Uses Selective post-emergence herbicide for control of a wide range of broad-leaved weeds, including triazine-resistant weeds, in maize. Application rates 125–250 g/ha. Compatibility Combination with 2,4-D increases effcacy and widens the weed spectrum. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Non-irritating to skin and slightly irritating to eyes (rabbits). NOEL (2 y) for rats 75 ppm (4.4 mg/kg b.w.) (EPA Tracking). ADI/RfD (EPA) 0.04 mg/kg b.w. [1993]. Other Non-mutagenic in the Ames Test. ENVIRONMENTAL FATE: Soil/Environment DT 50 in soil 4 h (under irradiation), 8 h (in the dark). Low mobility in sandy loam soil. NHCON CH 3 OCH 3 O CH 3 CH 3 CH 3 CH 3 O O Supplementary Entries – Extended metolcarb 383 metolcarb Insecticide IRAC 1A; carbamate NOMENCLATURE: Common name metolcarb (BSI, E-ISO); mé(tolcarb) ((m) F-ISO); MTMC (JMAF) IUPAC name m-tolyl methylcarbamate Chemical Abstracts name 3-methylphenyl methylcarbamate CAS RN [1129–41–5] EC no 214–446–0 Development codes C-3 (Nihon Nohyaku) Smiles code CNC(=O)Oc1cccc(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 165.2 M.f. C 9 H 11 NO 2 Form Tech. is a colourless solid. M.p. 76–77 °C; 74–75 °C (tech.) V.p. 145 mPa (20 °C) Solubility In water 2.6 g/l (30 °C). Soluble in polar organic solvents e.g. in cyclohexanone 790, xylene 100 (both in g/ kg, 30 °C), methanol 880 g/kg (room temperature). Sparingly soluble in non-polar solvents. COMMERCIALISATION: History Insecticide introduced by Nihon Nohyaku Co., Ltd and by Sumitomo Chemical Co., Ltd. Manufacturers Hunan Haili; Saeryung APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide with contact and respiratory action. Uses Control of planthoppers, leafhoppers, and other sucking insects on rice. Also used for control of citrus mealybugs, onion thrips, Mediterranean fruit fies, pink bollWorms and cotton aphids. Formulation types DP; EC; MG; WP. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Metacrate’* (Sumitomo Chemical); ‘Tsumacide’* (Nihon Nohyaku); Discontinued mixtures ‘Ofunack M’* (+ pyridaphenthion) (Mitsui Chemicals Agro). ANALYSIS: Product analysis by glc or by hplc (S. Sakaue et al., Nippon Nogei Kagaku Kaishi, 1981, 55, 1237). Residues determined by glc of a derivative with ECD (J. Miyamoto et al., Nihon Noyaku Gakkaishi, 1978, 3, 119). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). CH 3 O C O NHCH 3 384 The Pesticide Manual Sixteenth Edition © BCPC 2012 metsulfovax MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 580, female rats 498, mice 109 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Inhalation LC 50 for rats 0.475 mg/l air. Toxicity Class WHO (a.i.) II EC Classifcation Xn; R22| N; R51, R53 ECOTOXICOLOGY: Fish Low toxicity to fsh. ENVIRONMENTAL FATE: Animals Metabolism of carbamate insecticides is reviewed (M. Cool & C. K. Jankowski in Insecticides). metsulfovax Fungicide NOMENCLATURE: Common name metsulfovax (BSI, ANSI, E-ISO, (m) F-ISO) IUPAC name 2,4-dimethyl-1,3-thiazole-5-carboxanilide; 2,4-dimethylthiazole-5- carboxanilide Chemical Abstracts name 2,4-dimethyl-N-phenyl-5-thiazolecarboxamide CAS RN [21452–18–6] Development codes G696 Smiles code Cc1nc(C)c(s1)C(=O)Nc2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 232.3 M.f. C 12 H 12 N 2 OS Form Crystals. M.p. 140–142 °C V.p. 0.0017 mPa (25 °C) S.g./density 1.27 Solubility In water 342 mg/l. In hexane 0.32, methanol 171, toluene 12.9 (all in g/l). pKa 2.05 COMMERCIALISATION: History Fungicide evaluated by Uniroyal Chemical Co., Inc. APPLICATIONS: Biochemistry Inhibitor of succinate dehydrogenase complex, in the respiratory electron transport chain. Mode of action Systemic fungicide. Uses Control of Puccinia, Ustilago, Rhizoctonia solani, Tilletia spp., and other Basidiomycetes in cereals, cotton, potatoes, and ornamentals. Applied to foliage or as a seed treatment at 20–80 g/100 kg seed or up to 1 kg/ha foliar application. Formulation types FS; SC. WS . PRODUCTS: Discontinued products ‘Provax’* (Uniroyal). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 3929 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Inhalation LC 50 (4 h) for rats >5.7 mg/l air. NOEL (2 y) for female rats 50 mg/kg diet, for male rats 400 mg/kg diet. ADI/RfD (BfR) 0.025 mg/kg b.w. [1991]. Supplementary Entries – Extended mexacarbate 385 Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks >5620 mg/kg diet. Fish LC 50 (96 h) for bluegill sunfsh 34 mg/l. Daphnia LC 50 (48 h) >97 mg/l. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 c. 7 d. mexacarbate Acaricide, insecticide NOMENCLATURE: Common name mexacarbate (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name 4-dimethylamino-3,5-xylyl methylcarbamate Chemical Abstracts name 4-(dimethylamino)-3,5-dimethylphenyl methylcarbamate CAS RN [315–18–4] EC no 206–249–3 Development codes Dowco 139 Smiles code CNC(=O)Oc1cc(C)c(N(C)C)c(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 222.3 M.f. C 12 H 18 N 2 O 2 M.p. 85 °C V.p. 1.33 × 10 4 mPa Solubility In water 1000 ppm (25 °C). In xylene 5.1 × 10 4 , benzene 1.02 × 10 5 , ethanol 1.16 × 10 5 , acetone 1.16 × 10 5 (all in ppm, 25 °C). COMMERCIALISATION: History Insecticide introduced by Dow Chemical Co. (later DowElanco). APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Zectran’* (DowElanco). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). IARC 12 (1976). MAMMALIAN TOXICOLOGY: IARC Class 3 Toxicity Class WHO (a.i.) O EC Classifcation T+; R28| Xn; R21| N; R50, R53 386 The Pesticide Manual Sixteenth Edition © BCPC 2012 milneb MG 191 Herbicide safener NOMENCLATURE: IUPAC name 2-dichloromethyl-2-methyl-1,3-dioxolane CAS RN [22052–63–7] Development codes MG 191 Smiles code CC1(OCCO1) C(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 171.0 M.f. C 5 H 8 Cl 2 O 2 B.p. 91–92 °C /4 kPa K ow logP = 1.24 Solubility In water 9.75 g/l. Soluble in protic and aprotic organic solvents. Stability Stable 24 w at 54 °C; stable 40 w at 10 klux (25 °C). Stable to hydrolysis at pH 4, 6 and 8. COMMERCIALISATION: History Reported by F. Dutka et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1987, 1, 77–84). Herbicide safener developed by Nitrokémia Ipartelepek. APPLICATIONS: Biochemistry Increases glutathione synthesis and glutathione-related enzyme activity in protected plants. Mode of action Readily absorbed by maize roots and translocated. Uses A safener for thiocarbamate herbicides. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 465, female rats 492, male and female mice 653 mg/kg. milneb Fungicide NOMENCLATURE: Common name milneb (BSI, ANSI); thiadiazine (JMAF) IUPAC name 4,4′,6,6′-tetramethyl-3,3′-ethylenedi-1,3,5-thiadiazinane-2-thione Chemical Abstracts name 3,3′-(1,2-ethanediyl)bis[tetrahydro-4,6-dimethyl-2H- 1,3,5-thiadiazine-2-thione] CAS RN [3773–49–7] Development codes Experimental Fungicide 328 Smiles code CC1NC(C)N(CCN 2 C(C)NC(C)SC2=S)C(=S)S1 PHYSICAL CHEMISTRY: Mol. wt. 350.6 M.f. C 12 H 22 N 4 S 4 COMMERCIALISATION: History Fungicide evaluated by E. I. du Pont de Nemours & Co. PRODUCTS: Discontinued products ‘Banlate’* (DuPont). O O CH 3 CHCl 2 Supplementary Entries – Extended mirex 387 mipafox Acaricide, insecticide NOMENCLATURE: Common name mipafox (BSI, E-ISO, (m) F-ISO) IUPAC name N,N′-diisopropylphosphorodiamidic fuoride Chemical Abstracts name N,N′-bis(1-methylethyl)phosphorodiamidic fuoride CAS RN [371–86–8] EC no 206–742–3 Development codes Pestox 15 Smiles code CC(C)NP(=O)(F)NC(C)C PHYSICAL CHEMISTRY: Mol. wt. 182.2 M.f. C 6 H 16 FN 2 OP COMMERCIALISATION: History Insecticide and acaricide introduced by Pest Control Ltd (later Schering Agrochemicals). PRODUCTS: Discontinued products ‘Isopestox’* (Schering). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T+; R39/26/27/28 mirex Insecticide NOMENCLATURE: Common name mirex (ESA) IUPAC name dodecachloropentacyclo[5.3.0.02,6.03,9.04,8] decane; perchloropentacyclo[5.3.0.02,6.03,9.04,8]decane; dodecachloropentacyclo[5.2.1.02,6.03,9.05,8]decane Chemical Abstracts name 1,1a,2,2,3,3a,4,5,5,5a,5b,6-dodecachlorooctahydro-1,3,4- metheno-1H-cyclobuta[cd]pentalene Other names perchlordécone CAS RN [2385–85–5] EC no 219–196–6 Development codes GC 1283 (Allied) Smiles code ClC1(C2(Cl)C3(Cl)C4(Cl)C5(Cl)C1(Cl)C3(Cl)Cl)C5(Cl)C(Cl)(Cl)C24Cl PHYSICAL CHEMISTRY: Mol. wt. 545.5 M.f. C 10 Cl 12 V.p. 0.1 mPa (Residue Reviews, 103, 1 (1988)) Solubility In water 7 × 10 –5 ppm (22 °C) (Residue Reviews, 103, 1 (1988)). In dioxane 1.53 × 10 5 , benzene 1.22 × 10 5 , carbon tetrachloride 7.2 × 10 4 , methyl ethyl ketone 5.6 × 10 4 (all in ppm, room temperature). COMMERCIALISATION: History Insecticide introduced by Allied Chemical Corp., Agricultural Div. (later Hopkins Ltd). APPLICATIONS: Mode of action Ingested insecticide. 388 The Pesticide Manual Sixteenth Edition © BCPC 2012 monalide PRODUCTS: Discontinued products ‘Dechlorane’* (Allied); ‘Mirex’* (Seppic). ANALYSIS: Residues determined by glc with ECD, tlc or paper chromatography (AOAC Methods, 18th Ed., 977.19, 980.22, 970.52). See also Pestic. Anal. Man., I, 303. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 44 (1984). HSG 39 (1990). IARC 20 (1979). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEEC, as amended by Regulation 850/2004. MAMMALIAN TOXICOLOGY: IARC Class 2B NOEL NOAEL for rats 1 ppm (0.07 mg/kg b.w.) (EPA IRIS). ADI/RfD (EPA) cRfD 0.0002 mg/kg b.w. [1992]. Water GV Excluded from GV derivation (U). Toxicity Class WHO (a.i.) O EC Classifcation R40| R62, R63| R64| Xn; R21/22| N; R50, R53 MNFA Acaricide NOMENCLATURE: Common name MNFA (JMAF) IUPAC name 2-fuoro-N-methyl-N-1-naphthylacetamide Chemical Abstracts name 2-fuoro-N-methyl-N-(1-naphthalenyl)acetamide CAS RN [5903–13–9] Development codes NA-26 Smiles code CN(C(=O)CF)c1cccc2ccccc12 PHYSICAL CHEMISTRY: Mol. wt. 217.2 M.f. C 13 H 12 FNO COMMERCIALISATION: History Acaricide introduced by Nippon Soda Co., Ltd. PRODUCTS: Discontinued products ‘Nissol’* (Nippon Soda). monalide Herbicide NOMENCLATURE: Common name monalide (BSI, E-ISO, (f) F-ISO) IUPAC name 4′-chloro-2,2-dimethylvaleranilide; 4′-chloro-α,α-dimethylvaleranilide Chemical Abstracts name N-(4-chlorophenyl)-2,2-dimethylpentanamide CAS RN [7287–36–7] Development codes Schering 35 830 (AgrEvo) Supplementary Entries – Extended monisouron 389 Smiles code CCCC(C)(C)C(=O)Nc1ccc(Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 239.7 M.f. C 13 H 18 ClNO Form Colourless crystals. M.p. 87–88 °C V.p. 0.24 mPa (25 °C) Henryc. 2.52 × 10 –3 Pa m 3 mol –1 (calc.) Solubility In water 22.8 mg/l (23 °C). In cyclohexanonec. 500, xylene 100, petroleum ether <10 (all in g/l, 23 °C). Stability Stable to at least 50 °C and to hydrolysis (room temperature) at pH 7; DT 50 154 d (pH 5), 116 d (pH 8.95). COMMERCIALISATION: History Herbicide reported by F. Arndt (Z. Pfanzenkr. Pfanzenpathol. Pfanzenschutz, 1965, Sonderheft III, p. 277). Introduced by Schering AG (later AgrEvo GmbH). Patents GB 971819 APPLICATIONS: Mode of action Selective, systemic herbicide, absorbed by the leaves and roots. Uses Post-emergence control of broad-leaved weeds in umbelliferous crops, such as carrots, parsley, celery, and dill at 4 kg /ha . Formulation types EC. PRODUCTS: Discontinued products ‘Potablan’* (AgrEvo). ANALYSIS: Product analysis by hplc. Residues determined by glc after hydrolysis to 4-chloroaniline and bromination. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >4000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and rabbits >800 mg a.i. (as EC)/kg. NOEL (28 d) for rats 150 mg/kg daily. Toxicity Class WHO (a.i.) U EPA (formulation) III ECOTOXICOLOGY: Fish LC 50 for guppies >100 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Soil/Environment In soil (laboratory conditions) DT 50 30 d (pH 4.85), 48 d (pH 5.2), 59 d (pH 10.8). Degradation is presumably by ring hydroxylation, degradation to the aniline derivative, and ring opening. Duration of residual activity in soil isc. 6–8 weeks. monisouron Herbicide NOMENCLATURE: Common name monisouron (BSI, E-ISO, (m) F-ISO) IUPAC name 1-(5-tert-butyl-1,2-oxazol-3-yl)-3-methylurea; 1-(5-tert-butylisoxazol-3-yl)- 3-methylurea 390 The Pesticide Manual Sixteenth Edition © BCPC 2012 monuron; monuron-TCA Chemical Abstracts name N-[5-(1,1-dimethylethyl)-3-isoxazolyl]-N′-methylurea CAS RN [55807–46–0] Development codes SSH-41 Smiles code CNC(=O)Nc1cc(on1)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 197.2 M.f. C 9 H 15 N 3 O 2 COMMERCIALISATION: History Herbicide introduced by Shionogi & Co., Ltd. monuron; monuron-TCA Herbicide NOMENCLATURE: Common name monuron (BSI, E-ISO, F-ISO, ANSI, WSSA); monuron-TCA (WSSA for the trichloroacetate salt (ii)); chlorfenidim* (former exception, USSR); CMU (JMAF) IUPAC name 3-(4-chlorophenyl)-1,1-dimethylurea (i); 3-(4-chlorophenyl)-1,1- dimethyluronium trichloroacetate (ii) Chemical Abstracts name N′-(4-chlorophenyl)-N,N-dimethylurea (i); trichloroacetic acid compound with N′-(4-chlorophenyl)-N,N-dimethylurea (1:1) (ii); 3-(p-chlorophenyl)- 1,1-dimethylurea (i) CAS RN [150–68–5] monuron (i); [140–41–0] monuron- TCA (ii) EC no 205–766–1 (i) Development codes GC-2996 (Allied) (for (ii)) Smiles code monuron:CN(C)C(=O)Nc1ccc(Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 198.7; (monuron-TCA 362.0) M.f. C 9 H 11 ClN 2 O (monuron); C11H 12 Cl4N 2 O3 (monuron-TCA) Form Monuron and monuron-TCA are crystalline solids. M.p. 174–175 °C; (monuron-TCA 78–81 °C) V.p. 0.067 mPa (25 °C) (monuron) K ow logP = 1.46, 2.12 (Agchem. Desk Ref.) Henry 5.79 × 10 –5 Pa m 3 mol –1 (25 °C, calc.) S.g./density 1.27 (20 °C) Solubility Monuron: In water 230 mg/l (25 °C). In acetone 52 g/kg (27 °C); sparingly soluble in petroleum oils and in polar organic solvents. Monuron-TCA: In water 918 mg/l (room temperature). In 1,2-dichloroethane 400, methanol 177, xylene 91 (all in g/kg, room temperature). Stability Decomposes at 185–200 °C; rate of hydrolysis at room temperature and pH 7 negligible, but increases at elevated temperatures and under acidic or alkaline conditions. COMMERCIALISATION: History Herbicidal activity of monuron reported by H. C. Bucha & C. W. Todd (Science, 1951, 114, 493). Introduced by E. I. du Pont de Nemours & Co. and, as the trichloroacetate, by Allied Chemical Corp., Agricultural Division (later Hopkins Agricultural Chemical Co.). Patents US 2655445; GB 691403; GB 692589; US 2782112; US 2801911 Manufacturers Hermania APPLICATIONS: Biochemistry Photosynthesis inhibitor. Mode of action Total herbicide, absorbed via the roots. Uses It was recommended at 10–30 kg/ha for total weed control in non-crop areas; 5–10 kg/ha for annual maintenance. Monuron-TCA was used at 10–15 kg/ha for total Supplementary Entries – Extended morfamquat dichloride; morfamquat 391 weed control of uncropped areas. Formulation types WP (monuron). Compatibility Acidic in reaction and incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Telvar’* ((i)) (DuPont); ‘Urox’* ((ii)) (Allied). ANALYSIS: Product analysis of monuron by hydrolysis and titration of the liberated amine (CIPAC Handbook, 1980, 1A, 1310) and of monuron-TCA by i.r. spectrometry. Impurities determined by tlc (ibid., 1994, F, 336). Residues of monuron determined by glc (Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 664) or by hplc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: IARC 53 (1991). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Monuron: Acute oral LD 50 for rats 3600 mg/kg. Monuron-TCA: Acute oral LD 50 for rats 2300–3700 mg (in corn oil)/kg. Skin and eye Application of monuron to intact or abraded skin of guinea-pigs produced no irritation or sensitisation. Monuron-TCA is irritating to skin and mucous membranes. NOEL for rats and dogs 250–500 mg/kg diet (M C. Hodge et al., AMA Arch. Ind. Health, 1958, 17, 45). Toxicity Class WHO (a.i.) U (also for monuron-TCA) EC Classifcation R40| Xn; R22| N; R50, R53 (i): R40| Xi; R36/38| N; R50, R53 (ii) ENVIRONMENTAL FATE: Soil/Environment Slowly decomposed in moist soils. morfamquat dichloride; morfamquat Herbicide NOMENCLATURE: Common name morfamquat (BSI, E-ISO, (m) F-ISO) IUPAC name 1,1′-bis(3,5-dimethylmorpholinocarbonylmethyl)-4,4′-bipyridinium Chemical Abstracts name 1,1′-bis[2-(3,5-dimethyl-4-morpholinyl)-2-oxoethyl]- 4,4′-bipyridinium CAS RN [4636–83–3] morfamquat dichloride EC no 225–062–8 morfamquat dichloride Development codes PP745 PHYSICAL CHEMISTRY: Mol. wt. 468.6; (morfamquat dichloride 539.5) M.f. C 26 H 36 N 4 O 4 ; (morfamquat dichloride C26H36Cl 2 N4O4) COMMERCIALISATION: History Dichloride introduced as herbicide (H. M. Fox, Proc. Br. Weed Control Conf., 7th, 1964, 29; H. M. Fox & C. R. Beech, ibid., p. 108) by ICI Plant Protection Div. (later ICI Agrochemicals). 392 The Pesticide Manual Sixteenth Edition © BCPC 2012 mucochloric anhydride APPLICATIONS: Mode of action Systemic herbicide. PRODUCTS: Discontinued products ‘Morfoxone’* (ICI). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22| Xi; R36/37/38| R52, R53 (assigned to morfamquat and to its dichloride) morphothion Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name morphothion (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name O,O-dimethyl S-morpholinocarbonylmethyl phosphorodithioate Chemical Abstracts name O,O-dimethyl S-[2-(4-morpholinyl)-2-oxoethyl] phosphorodithioate CAS RN [144–41–2] EC no 205–628–0 Smiles code COP(=S)(OC)SCC(=O)N1CCOCC1 PHYSICAL CHEMISTRY: Mol. wt. 285.3 M.f. C 8 H 16 NO 4 PS 2 COMMERCIALISATION: History Systemic insecticide introduced by Sandoz AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide. PRODUCTS: Discontinued products ‘Ekatin M’* (Sandoz). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). MAMMALIAN TOXICOLOGY: EC Classifcation T; R23/24/25| N; R50, R53 mucochloric anhydride Fungicide NOMENCLATURE: IUPAC name 2,2′,3,3′-tetrachloro-4,4′-oxydibut-2-en-4-olide; 5,5′-oxybis(3,4-dichloro- 5H-furan-2-one) Chemical Abstracts name 5,5′-oxybis[3,4-dichloro-2(5H)-furanone] Supplementary Entries – Extended myclozolin 393 Other names mucochloric anhydride CAS RN [4412–09–3] Development codes GC 2466 Smiles code ClC1=C(Cl)C(=O)OC1OC2OC(=O)C(=C2Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 319.9 M.f. C 8 H 2 Cl 4 O 5 COMMERCIALISATION: History Fungicide reported by A. E. Rich (Plant Dis. Rep., 1960, 44, 306). Evaluated by Allied Chemical Corp., Agrochemical Div. (later Hopkins Ltd). myclozolin Fungicide NOMENCLATURE: Common name myclozoline ((f) F-ISO); myclozolin (BSI, E-ISO) IUPAC name (RS)-3-(3,5-dichlorophenyl)-5-methoxymethyl-5-methyl-1,3-oxazolidine- 2,4-dione Chemical Abstracts name 3-(3,5-dichlorophenyl)-5-(methoxymethyl)-5-methyl-2,4- oxazolidinedione CAS RN [54864–61–8] Development codes BAS 436F (BASF) Smiles code COCC1(C)OC(=O)N(C1=O)c2cc(Cl)cc(Cl)c2 PHYSICAL CHEMISTRY: Mol. wt. 304.1 M.f. C 12 H 11 Cl 2 NO 4 Form Colourless crystalline solid. M.p. 111 °C V.p. 0.059 mPa (20 °C) Henry 2.68 × 10 –3 Pa m 3 mol –1 (calc.) Solubility In water 6.7 mg/kg (20 °C). In chloroform 400, ethanol 20 (both g/kg, 20 °C). Stability Hydrolysed under alkaline conditions. COMMERCIALISATION: History Fungicide reported by E-H. Pommer & B. Zeeh (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1982, 47, 935). Introduced by BASF AG. Patents DE 2324591 APPLICATIONS: Mode of action Contact fungicide. Uses Diseases caused by Botrytis, monilia, sclerotinia spp. are controlled on beans, cucumbers, grapes, groundnuts, lettuce, oilseed rape, ornamentals, stone fruit, strawberries, sunfowers, tomatoes. Formulation types SC. WP. ANALYSIS: Product analysis is by glc with FID. Residues may be determined by glc with ECD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Toxicity Class WHO (a.i.) U 394 The Pesticide Manual Sixteenth Edition © BCPC 2012 naphthalic anhydride naphthalene Fungicide, insecticide NOMENCLATURE: Common name naphtalé(ne) (F-ISO); naphthalene (BSI, E-ISO, accepted in lieu of a common name) IUPAC name naphthalene (I) Chemical Abstracts name (I) CAS RN [91–20–3] Smiles code c1ccc2ccccc2c1 PHYSICAL CHEMISTRY: Mol. wt. 128.2 M.f. C 10 H 8 Form Colourless faky crystals. M.p. 80 °C B.p. 218 °C V.p. 6500 mPa (20 °C) Henry 2.78 × 101 Pa m 3 mol –1 (calc.) S.g./density 1.517 (15 °C) Solubility In water 30 mg/l (room temperature). In benzene, toluene 285, carbon tetrachloride, chloroform 500, ethanol, methanol 77 (all in g/l). Very soluble in 1,2-dichloroethane, diethyl ether. F.p. 79 °C (open cup), 88 °C (closed cup) COMMERCIALISATION: History Has long been used as a household fumigant against clothes moths. APPLICATIONS: Mode of action Fumigant insecticide. Uses Its effectiveness as a household fumigant against clothes moths has been questioned (W. S. Abbott & S. C. Billings, J. Econ. Entomol., 1935, 28, 493). Has been used as a fumigant against soil fungi, but is rapidly decomposed by soil micro-organisms. ANALYSIS: Product analysis by distillation from mixtures in the presence of ethanol and precipitation as the picrate (D. S. Binnington & W. F. Giddes, Ind. Eng. Chem. Anal. Ed., 1934, 6, 461; W. L. Millar, J. Assoc. Off. Agric. Chem., 1934, 17, 308). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.667 (2005). IARC 82 (2002). EU Status (1107/2009) Not approved, 2004/129/EC. MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 2200 mg/kg. NOEL NOAEL for rats 71 mg/kg daily (EPA IRIS). ADI/RfD (EPA) aRfD 0.4 mg/kg b.w., cRfD 0.1 mg/kg b.w. [2008]. Toxicity Class WHO (a.i.) U; (WHO Recommended Classifcation gives O) EC Classifcation R40| Xn; R22| N; R50, R53 naphthalic anhydride Herbicide safener NOMENCLATURE: Common name naphthalic anhydride (draft E-ISO, is used in lieu of common name) IUPAC name naphthalene-1,8-dicarboxylic anhydride Chemical Abstracts name 1H,3H-naphtho[1,8-cd]pyran-1,3-dione CAS RN [81–84–5] Supplementary Entries – Extended naphthalic anhydride 395 Smiles code O=C1OC(=O)c2cccc3cccc1c23 PHYSICAL CHEMISTRY: Composition Tech. is ≥98%. Mol. wt. 198.2 M.f. C 12 H 6 O 3 Form Light tan crystalline solid. M.p. 270–274 °C Solubility Relatively insoluble in water and most non-polar solvents; in DMF 13.9 g/l. Stability Stable under normal storage conditions; non- hygroscopic. COMMERCIALISATION: History Enhancement of the selectivity of thiocarbamate herbicides to maize reported by O. L. Hoffman (Weed Sci. Soc. Am., Abstr., 1969, No. 12) and reviewed by G. R. Stephenson & F. Y. Chang (in Chem. Action Herbic. Antid., p. 35). Introduced by Gulf Oil Corp. Patents US 3131509; US 3564768 APPLICATIONS: Biochemistry Enhances cytochrome P450-mediated oxidative metabolism of the herbicide, and its subsequent conjugation (see J. Davies & J. C. Caseley, Pestic. Sci. 1999, 55(11) 1043–1058). Uses Used as a seed coating, at 5 g/kg seed, prior to planting and protects maize from damage by EPTC, vernolate and related thiocarbamate herbicides. Germination of maize seed planted 2 y after treatment was not affected. Formulation types TC. PRODUCTS: Discontinued products ‘Protect’* (Gulf). ANALYSIS: Residues in crops determined by glc with ECD (J. R. Riden, Anal. Methods Pestic. Plant Growth Regul., 1976, 8, 483). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 12 300 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2025 mg/kg. Moderate irritant to eyes of albino rabbits. Inhalation Inhalation of the dust by rats for 4 h at 820 mg/m 3 air revealed no toxic symptom. NOEL In 90 d feeding trials, no ill-effect noted for rats and dogs receiving 500 mg/kg diet. Toxicity Class WHO (a.i.) U 396 The Pesticide Manual Sixteenth Edition © BCPC 2012 naproanilide naproanilide Herbicide HRAC K3 WSSA 15; alkanamide (acetamide) NOMENCLATURE: Common name naproanilide (JMAF) IUPAC name 2-(2-naphthyloxy)-N-phenylpropionamide Chemical Abstracts name 2-(2-naphthalenyloxy)-N-phenylpropanamide CAS RN [52570–16–8] unstated stereochemistry Development codes MT-101 (Mitsui Toatsu) Smiles code CC(Oc1ccc2ccccc2c1)C(=O)Nc3ccccc3 PHYSICAL CHEMISTRY: Mol. wt. 291.3 M.f. C 19 H 17 NO 2 Form Whitish crystals. M.p. 128 °C V.p. 2.8 × 10 –6 mPa (20 °C) S.g./density 1.256 (25 °C) Solubility In water 0.75 mg/l (27 °C). In acetone 171, toluene 42, ethanol 17, benzene 46 (all in g/l, 27 °C). Stability Dilute aqueous solutions slowly degraded by uv light; solid stable to light. F.p. 110 °C COMMERCIALISATION: History Herbicide reported by S. Fujisawa (Jpn. Pestic. Inf., 1981, No. 39, p. 19). Introduced by Mitsui Toatsu Chemicals, Inc. (later Mitsui Chemicals, Inc.). APPLICATIONS: Biochemistry The active principle is thought to be the corresponding carboxylic acid. Mode of action Selective herbicide, absorbed through stems and roots. Uses Controls annual and some perennial weeds, but not Echinochloa crus-galli, in paddy rice, at 2–3 kg/ha. Gives good control of young Sagittaria pygmaea. Phytotoxicity Phytotoxic to direct seeding rice at high dosages. Formulation types GR . PRODUCTS: Discontinued products ‘Uribest’* (Mitsui Chemicals Agro). ANALYSIS: Product and residue analysis by hplc (Gotoh, J. Pestic. Sci., 1977, (4), p. 2). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >15 000, mice >20 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >3000, mice >5000 mg/kg. Toxicity Class EPA (formulation) IV ECOTOXICOLOGY: Fish TLm (72 h) >100 ppm. Daphnia LC 50 (6 h) 40 mg/l. ENVIRONMENTAL FATE: Soil/Environment DT 50 in soil 2–7 d. CH C NH O O CH 3 Supplementary Entries – Extended naptalam 397 naptalam Herbicide HRAC P WSSA 19; phthalamate NOMENCLATURE: naptalam Common name NPA (JMAF, for sodium salt); alanap* (former exception, Turkey); naptalame ((m) F-ISO); naptalam (BSI, E-ISO, WSSA) IUPAC name N-1-naphthylphthalamic acid Chemical Abstracts name 2-[(1-naphthalenylamino)carbonyl]benzoic acid CAS RN [132–66–1] naptalam; [132–67–2] naptalam-sodium EC no 205–073–4 (naptalam-sodium) Smiles code OC(=O)c1ccccc1C(=O)Nc2cccc3ccccc23 PHYSICAL CHEMISTRY: naptalam Mol. wt. 291.3 (naptalam); 313.3 (naptalam-sodium) M.f. C 18 H 13 NO 3 ; sodium salt C18H 12 NNaO3 Form Crystalline solid. M.p. 185 °C V.p. <133 Pa (20 °C) K ow logP = 0.104 (pH 5), 0.004 (pH 7), –0.036 (pH 9); logP = 0.006 (naptalam-sodium, Uniroyal, via USDA ARS PPD) Henry <1.94 × 10 2 Pa m 3 mol –1 (calc.) S.g./density 1.36 (20 °C) Solubility In water 200 mg/l (20 °C). In acetone 5, DMF 39, DMSO 43, methyl ethyl ketone 4, isopropanol 2, carbon tetrachloride 0.1 (all in g/kg). Practically insoluble in benzene, hexane, and xylene. Sodium salt: In water 300 g/kg (20 °C). In acetone 17, DMF 50, methyl ethyl ketone 6, isopropanol 21, benzene 0.5, xylene 0.4 (all in g/kg). Stability Hydrolysis DT 50 7.1 d (pH 5), 2.4 y (pH 7), stable (pH 9) (all 20 °C); a second study shows DT 50 2.9 d (pH 5, 25 °C). pKa 4.6 COMMERCIALISATION: History Plant growth-regulating activity of N-arylphthalamic acids reported by O. L. Hoffman & A. E. Smith (Science, 1949, 109, 588). Naptalam-sodium introduced by Uniroyal Chemical Co., Inc. (became Chemtura Corp.) in 1955. Patents US 2556664; US 2556665 Manufacturers Chemtura APPLICATIONS: Biochemistry Inhibits indolylacetic acid transport. Mode of action Selective herbicide, absorbed predominantly by the roots, but also, to some extent, by the foliage, with accumulation in meristematic tissue. Inhibits seed germination. Uses Pre-emergence control of many broad-leaved weeds and some grasses in cucurbits, asparagus, peanuts, soya beans, and established woody ornamentals, at 2.0–5.5 kg/ha. Phytotoxicity Phytotoxic to beet, tomatoes, spinach, and lettuce. Formulation types GR; SL; WP. CO 2 H C NH O 398 The Pesticide Manual Sixteenth Edition © BCPC 2012 naptalam Compatibility Incompatible with pesticides which may cause amine transfer or replacement. PRODUCTS: naptalam Discontinued products ‘Aksol’* (DuPont); ‘Alanap’* (sodium salt) (Chemtura); ‘Alanap-L’* (sodium salt) (Chemtura); ‘Naptro’* (Crystal). ANALYSIS: Product analysis by uv spectrometry; details from Chemtura. Residues determined by hydrolysis to 1-naphthylamine, a derivative of which is measured by colorimetry (A. E. Smith & G. M. Stone, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 4, 1). See also Pestic. Anal. Man., II, 180.297. In soil, by hplc/ELCD (Environ. Chem. Methods). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: naptalam Oral Acute oral LD 50 for rats 1770 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >5000 mg/kg. Severe eye irritant; mild skin irritant (rabbits). Inhalation LC 50 (4 h) for rats >2.07 mg/l air. NOEL In chronic feeding trials, NOEL for rats 30, dogs 5 mg/kg b.w. daily. ADI/RfD (EPA) cRfD 0.258 mg/kg b.w. [2004]. Other Not a bacterial mutagen. Toxicity Class WHO (a.i.) U EPA (formulation) II (‘Alanap-L’) EC Classifcation Xn; R22 ECOTOXICOLOGY: naptalam Birds LD 50 for mallard ducks >4640 mg/kg. Dietary LC 50 (8 d) for mallard ducks and bobwhite quail >10 000 ppm. Fish LC 50 (96 h) for rainbow trout 76.1, bluegill sunfsh 354 ppm. Daphnia LC 50 (48 h) 118.5 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Plants In plants, naptalam rapidly breaks down into phthalic acid and 1-naphthylamine. Soil/Environment Duration of residual activity isc. 3–8 w, depending on soil type and moisture content (E. Smith et al., J. Agric. Food Chem., 1957, 5, 748). For sandy loam, adsorption Kd 14.98, K oc 2152. Supplementary Entries – Extended natamycin 399 natamycin Fungicide See also The Manual of Biocontrol Agents entry: 2:199 NOMENCLATURE: Common name natamycin (BAN); pimaricin (traditional name); tennecetin (traditional name) IUPAC name (8E,14E,16E,18E,20E)-(1R,3S,5R,7R,12R,22R,24S,25R,26S)-22-(3-amino- 3,6-dideoxy-β-D-mannopyranosyloxy)-1,3,26-trihydroxy-12-methyl-10-oxo-6,11,28- trioxatricyclo[22.3.1.05,7]octacosa-8,14,16,18,20-pentaene-25-carboxylic acid Chemical Abstracts name [1R-(1R*,3S*,5R*,7R*,8E,12R*,14E,16E,18E,20E,22R*,24S* 25R*,26S*)]-22-[(3-amino-3,6-dideoxy-β-D-mannopyranosyl)oxy]-1,3,26-trihydroxy-12- methyl-10-oxo-6,11,28-trioxatricyclo[22.3.1.05,7]octacosa-8,14,16,18,20-pentaene-25- carboxylic acid Other names myprozine CAS RN [7681–93–8] EC no 231–683–5 Smiles code CC1OC(OC2CC3OC(O)(CC(O)C3C(=O)O)CC(O)CC4OC4C=CC(=O) OC(C)CC=CC=CC=CC=C2)C(O)C(N)C1O PHYSICAL CHEMISTRY: Composition Exists as a trihydrate. Tech. is >87%. Mol. wt. 665.7 (anhydrous) M.f. C 33 H 47 NO 13 Form White crystals. M.p. 280–300 °C (decomp.) Solubility In water 4.1 g/l (20–22 °C). In DMSO >200, methanol 97, ethanol 5.5, acetone 0.85, petroleum spirit 0.1, benzene 0.05 (all in g/l, 20–22 °C) (J. R. Marsh & P. J. Weiss, J. Assoc. Off. Anal. Chem., 1967, 50, 457). Stability Stable when dry, but sensitive to light. Forms water-soluble salts with acids or alkalis. COMMERCIALISATION: Production By fermentation of Streptomyces natalensis and S. chattanoogensis. History Structure established by B. T. Golding et al. (Tetrahedron Lett., 1966, p. 3551), W. E. Meyer (Chem. Commun., 1968, p. 470) and G. Gaudiano et al. (Chem. Ind. (Milan), 1966, 48, 1327). Stereochemistry revised (J. M. Lancelin & J. M. Beau, J. Am. Chem. Soc., 1990, 112, 4060, 6749; A. J. Duplantier & S. Masamune, ibid., p. 7079). Introduced as a fungicide by Gist-Brocades N.V. Patents GB 712547; GB 844289; US 3892850 Manufacturers Gist- Brocades O O O HO HO O OH CO 2 H CH 3 O O HO NH 2 OH CH 3 400 The Pesticide Manual Sixteenth Edition © BCPC 2012 NC-170 APPLICATIONS: Uses Control of diseases of bulbs, especially basal rot (Fusarium oxysporum) of daffodils, preferably combined with a hot-water treatment. Formulation types WP. PRODUCTS: Discontinued products ‘Delvolan’* (Gist-Brocades). ANALYSIS: Product analysis is either by bioassay with a suitable micro-organism, and confrmed by the effect of the enzyme pimaricinase, or by uv spectrometry. Residues may be determined by bioassay. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2730–4670 mg/kg (G. J. Levinskas, Toxicol. Appl. Pharmacol., 1966, 8, 97). Skin and eye No acute toxicity, even at high doses. Not a skin or eye irritant (rabbits). Not a skin sensitiser. Toxicity Class WHO (a.i.) III ECOTOXICOLOGY: Fish Not toxic to fsh. ENVIRONMENTAL FATE: Readily biodegradable. NC-170 Insecticide NOMENCLATURE: IUPAC name 4-chloro-5-(6-chloro-3-pyridylmethoxy)-2-(3,4-dichlorophenyl)pyridazin- 3(2H)-one Chemical Abstracts name 4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4- dichlorophenyl)-3(2H)-pyridazinone CAS RN [107360–34–9] Development codes NC-170 Smiles code Clc1ccc(COc2cnn(c3ccc(Cl)c(Cl)c3)c(=O)c2Cl)cn1 PHYSICAL CHEMISTRY: Mol. wt. 417.1 M.f. C 16 H 9 Cl 4 N 3 O 2 M.p. 180–181 °C COMMERCIALISATION: History Insect growth regulator reported by T. Miyake et al. (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., 2, 535). Evaluated by Nissan Chemical Industries Ltd. APPLICATIONS: Uses Evaluated for control of hoppers in rice. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Not irritating to skin or eyes (rabbits). ECOTOXICOLOGY: Daphnia LC 50 >1 mg/l. Supplementary Entries – Extended NC-330 401 NC-196 Insecticide NOMENCLATURE: IUPAC name 2-benzyl-5-[2-(ethoxycarbonylamino)ethoxy]-pyridazin-3(2H)-one Chemical Abstracts name ethyl [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl] oxy]ethyl]carbamate CAS RN [133456–86–7] Development codes NC-196 PHYSICAL CHEMISTRY: Mol. wt. 317.3 M.f. C 16 H 19 N 3 O 4 M.p. 73.5–78.0 °C COMMERCIALISATION: History Reported by T. Miyake et al. (Proc. Br. Crop Prot. Conf., Pests Dis. - 1994, 1, 59). Manufacturers Nissan APPLICATIONS: Mode of action Juvenile hormone mimic, also with ovicidal properties. Active by contact and as a soil drench. Uses Evaluated for control of Brown planthopper (Nilaparvata lugens) and diamond-back moth (Plutella xylostella) in rice. Formulation types GR . MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 2322, female rats 1296, male mice 982, female mice 1355 mg/kg. Skin and eye Acute percutaneous LD 50 for female rabbits >5000 mg/kg. Slight eye irritant, not a skin irritant (rabbits). Other Negative in Ames, micronucleus and Rec tests. ECOTOXICOLOGY: Fish LC 50 (48 h) for carp and rainbow trout >40 mg/l. Daphnia LC 50 (48 h) >40 mg/l. NC-330 Herbicide NOMENCLATURE: IUPAC name methyl 5-(4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl)-1-(2-pyridyl) pyrazole-4-carboxylate CAS RN [104770–29–8] Development codes NC-330; NCI-851013 (both Nissan) Smiles code COC(=O)c1cnn(c1S(=O)ONC(=O)Nc2nc(C)cc(C)n2)c3ccccn3 PHYSICAL CHEMISTRY: Mol. wt. 431.4 M.f. C 17 H 17 N 7 O 5 S Form Pale brownish solid. M.p. 159–160 °C Solubility In water 849 mg/l (25 °C). SO 2 NHCONH N N CH 3 CH 3 N N CO 2 Me N 402 The Pesticide Manual Sixteenth Edition © BCPC 2012 nickel bis(dimethyldithiocarbamate) COMMERCIALISATION: History Herbicide reported by T. Nawamaki et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1991, 1, 45). Developed by Nissan Chemical Industries Ltd. Manufacturers Nissan APPLICATIONS: Biochemistry Branched chain amino acid synthesis (ALS or AHAS) inhibitor. Acts by inhibiting biosynthesis of the essential amino acids valine and isoleucine, hence stopping cell division and plant growth. Selectivity derives from rapid metabolism in the crop. Metabolic basis of selectivity in sulfonylureas reviewed (M. K. Koeppe & H. M. Brown, Agro- Food-Industry, 1995, 6, 9–14). Mode of action Systemic herbicide, absorbed mainly by the foliage and translocated to meristem tissues. Uses Control of grass and broad-leaved weeds post-emergence in winter wheat, at 100–150 g/ha. Phytotoxicity Phytotoxic to winter barley. ANALYSIS: Residues of sulfonylureas in soil and water may be determined by immunoassay (Environ. Chem. Methods). Methods for sulfonylurea residues in crops, soil and water reviewed (A. C. Barefoot et al., Proc. Br. Crop Prot. Conf. – Weeds, 1995, 2, 707). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >5000 mg/kg. Skin and eye Non-irritating to skin; mild eye irritant (rabbits). Other Non-mutagenic in the Ames test. ECOTOXICOLOGY: Fish LC 50 (48 h) for carp >5 mg/l. nickel bis(dimethyldithiocarbamate) Bactericide, fungicide NOMENCLATURE: IUPAC name nickel bis(dimethyldithiocarbamate) Chemical Abstracts name nickel dimethylcarbamodithioate Other names organic nickel (JMAF) CAS RN [15521–65–0] Development codes M-1; DDC-Ni Smiles code [Ni+2].CN(C)C(=S)[S-].CN(C)C(=S)[S-] PHYSICAL CHEMISTRY: Composition Tech. is ≥96%. Mol. wt. 299.1 M.f. C 6 H 12 N 2 NiS 4 Form Green, amorphous powder. M.p. Decomposes above 250 °C Solubility Practically insoluble in water. In (CH 3 ) 2 N C S S Ni 2 Supplementary Entries – Extended nifuridide 403 chloroform 287, DMF 560, tetrahydrofuran 475 (all in mg/l, 20 °C). Stability Stable in acidic and alkaline media at room temperature. COMMERCIALISATION: History Fungicide introduced by Mikasa Chemical Co. (who merged with Yashima Chemical Industry Co. Ltd in 1996) and frst registered in Japan in 1968. Manufacturers Yashima APPLICATIONS: Mode of action Foliar fungicide and bactericide with protective action. Uses Control of bacterial leaf blight and bacterial grain rot in paddy rice, at 1800–2400 g/ha. Formulation types DP; WP. PRODUCTS: Discontinued products ‘Sankel’* (Yashima). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 78 (1988) is a general review of dithiocarbamates and their degradation products. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >36 000, mice >30 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. NOEL (2 y) for rats 200 mg/kg diet. ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 360 mg/l. nifuridide Insecticide NOMENCLATURE: Common name nifuridide (BSI, ANSI, E-ISO, (m) F-ISO) IUPAC name 6′-amino-α,α,α,2,2,3,3-heptafuoro-5′-nitropropion-m-toluidide Chemical Abstracts name N-[2-amino-3-nitro-5-(trifuoromethyl)phenyl]-2,2,3,3- tetrafuoropropanamide CAS RN [61444–62–0] Development codes EL-468 Smiles code Nc1c(NC(=O)C(F)(F)C(F)F)cc(cc1[N+](=O)[O-])C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 349.2 M.f. C 10 H 6 F 7 N 3 O 3 COMMERCIALISATION: History Insecticide evaluated by Eli Lilly & Co. PRODUCTS: Discontinued products ‘Bant’* (Lilly). 404 The Pesticide Manual Sixteenth Edition © BCPC 2012 nithiazine nipyraclofen Herbicide NOMENCLATURE: Common name nipyraclofè(ne) ((m) F-ISO); nipyraclofen (BSI, E-ISO) IUPAC name 1-(2,6-dichloro-α,α,α-trifuoro-p-tolyl)-4-nitropyrazol-5-ylamine Chemical Abstracts name 1-[2,6-dichloro-4-(trifuoromethyl)phenyl]-4-nitro-1H- pyrazol-5-ylamine CAS RN [99662–11–0] Development codes SLA 3992 (Bayer) Smiles code Nc1c(cnn1c2c(Cl)cc(cc2Cl)C(F)(F)F)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 341.1 M.f. C 10 H 5 Cl 2 F 3 N 4 O 2 COMMERCIALISATION: History Herbicide discovered by Bayer AG. APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. nithiazine Insecticide IRAC 4A NOMENCLATURE: Common name nithiazine (BSI, E-ISO, (m) F-ISO, ANSI, not Japan) IUPAC name 2-nitromethylene-1,3-thiazinane Chemical Abstracts name tetrahydro-2-(nitromethylene)-2H-1,3-thiazine CAS RN [58842–20–9] Development codes IN-A0159 (DuPont); SD 35651 (Shell, DuPont) Smiles code [O-][N+](=O)C=C1NCCCS1 PHYSICAL CHEMISTRY: Mol. wt. 160.2 M.f. C 5 H 8 N 2 O 2 S Solubility In water 200 g/l (23 °C). COMMERCIALISATION: History Insecticide reported by S. B. Soloway et al. (Pestic. Venom Toxici. (Selected Papers Internat. Congr. Entomol., 15th, 1976), 1978, p. 153). Notable as original member of ‘nitromethylene’ group of insecticides. Evaluated originally by Shell Research Ltd, later E. I. du Pont de Nemours & Co. APPLICATIONS: Biochemistry Agonist of the nicotinic acetylcholine receptor, affecting the synapses in the insect central nervous system. NH S NO 2 CH Supplementary Entries – Extended nitralin 405 nitralin Herbicide NOMENCLATURE: Common name nitralin (BSI, E-ISO, (m) F-ISO, WSSA, JMAF) IUPAC name 4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline Chemical Abstracts name 4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylbenzenamine CAS RN [4726–14–1] Development codes SD 11 831 Smiles code CCCN(CCC)c1c(cc(cc1[N+](=O)[O-])S(=O)(=O)C)[N+](=O)[O-] PHYSICAL CHEMISTRY: Composition Tech. isc. 94%. Mol. wt. 345.4 M.f. C 13 H 19 N 3 O 6 S Form Tech. is a yellow powder. M.p. 151–152 °C (tech.) V.p. 0.002 mPa (25 °C) S.g./density 1.39 (20 °C, tech.) Solubility In water 0.6 mg/l (22 °C). In acetone 360, DMSO 330, 2-nitropropane 250 (all in g/l, 22 °C); sparingly soluble in common hydrocarbon and aromatic solvents and alcohols. Stability Contact of nitralin with concentrated bases, or temperatures >200 °C, should be avoided. COMMERCIALISATION: History Herbicide reported by J. B. Regan et al. (Proc. Northeast. Weed Control Conf., 1966, p. 36). Introduced by Shell Research Ltd. Patents BE 672199 APPLICATIONS: Mode of action Selective herbicide. Uses Used pre-em. to control annual grasses and many broad-leaved weeds in cotton, groundnuts, rape, soya beans and transplanted crops such as brassicas, tobacco, tomatoes at 0.5–0.75 kg/ha on light soils, 1.0–1.5 kg/ha on heavier soils (<5% o.m.); not used in highly organic or peat soils. Formulation types WP. PRODUCTS: Discontinued products ‘Planavin’* (Shell). ANALYSIS: Product analysis by i.r. spectrometry or by glc (Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 625). Residues determined by glc with ECD (ibid.). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >2000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. NOEL (2 y) for rats and dogs 2000 mg/kg diet. Toxicity Class WHO (a.i.) U ENVIRONMENTAL FATE: Soil/Environment Relatively immobile in soil; DT 50 c. 30–50 d. 406 The Pesticide Manual Sixteenth Edition © BCPC 2012 nitrilacarb; nitrilacarb 1:1 zinc chloride complex nitrilacarb; nitrilacarb 1:1 zinc chloride complex Acaricide, insecticide NOMENCLATURE: Common name nitrilacarb (BSI, E-ISO, ANSI, ESA); nitrilacarbe ((m) F-ISO) IUPAC name 4,4-dimethyl-5-(methylcarbamoyloxyimino)valeronitrile; 4,4-dimethyl-5- (methylcarbamoyloxyimino)pentanenitrile Chemical Abstracts name 4,4-dimethyl-5-[[[(methylamino)carbonyl]oxy]imino] pentanenitrile CAS RN [29672–19–3] nitrilacarb; [58270–08–9] 1:1 complex with zinc chloride, formerly [61332–32–9] Development codes AC 82 258 (zinc complex); CL 72 613 (nitrilacarb) PHYSICAL CHEMISTRY: Mol. wt. 197.2; (zinc chloride complex 333.5) M.f. C 9 H 15 N 3 O 2 ; (zinc chloride complex C 9 H15Cl 2 N3O 2 Zn) Form The tech. zinc chloride complex is an almost colourless powder. M.p. 120–125 °C (zinc chloride complex) S.g./ density 0.5 (zinc chloride complex) Solubility The zinc chloride complex is soluble in water, acetone, acetonitrile, alcohols; slightly soluble in chloroform; practically insoluble in benzene, diethyl ether, hexane, toluene, xylene. Stability The zinc chloride complex is very hygroscopic; stable ≥1.5 y (≤25 °C) when stored in original, unopened containers. COMMERCIALISATION: History Insecticide reported by W. K. Whitney & J. L. Aston (Proc. Br. Insectic. Fungic. Conf., 8th, 1975, 2, 633). The 1:1 complex with zinc chloride introduced by American Cyanamid Co. Patents US 3681505, US 3621049. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses Nitrilacarb was used against a range of phytophagous mites and aphids, also whitefies, thrips, leafhoppers at 25–75 g/100 l, and Leptinotarsa decemlineata, at 0.5 kg/ha. PRODUCTS: Discontinued products ‘Accotril’* (1:1 zinc chloride complex.) (Cyanamid); ‘Cyanotril’* (Cyanamid). ANALYSIS: Residues are determined by glc. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Supplementary Entries – Extended nitrofen 407 nitrofen Herbicide NOMENCLATURE: Common name NIP (JMAF); nitrofen (BSI, E-ISO, WSSA); nitrofè(ne) ((m) F-ISO); niclofen (Canada) IUPAC name 2,4-dichlorophenyl 4-nitrophenyl ether Chemical Abstracts name 2,4-dichloro-1-(4-nitrophenoxy)benzene CAS RN [1836–75–5] EC no 217–406–0 Development codes FW-925 Smiles code [O-][N+](=O)c1ccc(Oc2ccc(Cl)cc2Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 284.1 M.f. C 12 H 7 Cl 2 NO 3 Form Crystalline solid. M.p. 70–71 °C V.p. 1.06 mPa (40 °C) Solubility In water 0.7–1.2 mg/l (22 °C). COMMERCIALISATION: History Herbicide introduced by Rohm & Haas Co. Patents GB 974475; US 3080225 APPLICATIONS: Mode of action Selective herbicide. Uses Toxic to a number of broad-leaved and grass weeds, and effective when left as a thin layer on the soil surface; activity is rapidly lost on incorporation in soil. It was used for weed control in cereals pre-em. at 2 kg/ ha. Many vegetable crops tolerate applications pre-em. ≤3 kg/ha and post-em. ≤1 kg/ha. Formulation types EC; WP. PRODUCTS: Discontinued products ‘Tok’* (Rohm & Haas); ‘Tokkorn’* (Rohm & Haas). ANALYSIS: Product analysis by glc with FID (I. L. Adler & B. M. Jones, Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 403). Residues determined by glc with ECD of a derivative (idem, ibid.). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 41 (1983). PDS 84 (1996). ICSC.929 (1999). IARC 30 (1983). EU Status (1107/2009) Considered to be outside the scope of the Directive; already banned, 79/117/EEC as amended by 87/181/EEC. MAMMALIAN TOXICOLOGY: IARC Class tech. is 2B Oral Acute oral LD 50 for rats 638–888, rabbits 300–510 (both as mg a.i. (as EC)/kg). Skin and eye Neither the a.i. nor the formulations caused irritation to skin of rabbits or visible toxic effects. ADI/RfD (JMPR) No ADI [1983]. Other Women of child-bearing age should not be exposed to the product. Carcinogenic in rats and mice and is teratogenic in several species tested. Toxicity Class WHO (a.i.) Ia EC Classifcation R45| R61| Xn; R22| N; R50, R53 408 The Pesticide Manual Sixteenth Edition © BCPC 2012 4-(2-nitroprop-1-enyl)phenyl thiocyanate nitrofuorfen Herbicide NOMENCLATURE: Common name nitrofuorfen (BSI, E-ISO, ANSI, WSSA); nitrofuorfè(ne) ((m) F-ISO) IUPAC name 2-chloro-α,α,α-trifuoro-p-tolyl 4-nitrophenyl ether Chemical Abstracts name 2-chloro-1-(4-nitrophenoxy)-4-(trifuoromethyl)benzene CAS RN [42874–01–1] Development codes RH-2512 Smiles code [O-][N+](=O)c1ccc(Oc2ccc(cc2Cl)C(F)(F)F)cc1 PHYSICAL CHEMISTRY: Mol. wt. 317.7 M.f. C 13 H 7 ClF 3 NO 3 COMMERCIALISATION: History Herbicide evaluated by Rohm & Haas Co. APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. N-3-nitrophenylitaconimide Fungicide NOMENCLATURE: IUPAC name N-3-nitrophenylitaconimide Chemical Abstracts name 3-methylene-N-(3-nitrophenyl)pyrrolidine-2,5-dione CAS RN [4137–12–6] Development codes B 720 Smiles code [O-][N+](=O)c1cccc(c1)N 2 C(=O)CC(=C)C2=O PHYSICAL CHEMISTRY: Mol. wt. 232.2 M.f. C 11 H 8 N 2 O 4 COMMERCIALISATION: History Fungicide reported by B. von Schmeling (Phytopathology, 1962, 52, 819). Evaluated by Uniroyal Chemical Co., Inc. 4-(2-nitroprop-1-enyl)phenyl thiocyanate Fungicide NOMENCLATURE: Common name nitrostyrene (JMAF) IUPAC name 4-(2-nitroprop-1-enyl)phenyl thiocyanate Chemical Abstracts name 4-(2-nitro-1-propenyl)phenyl thiocyanate CAS RN [950–00–5] Smiles code CC(=Cc1ccc(SC#N)cc1)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 220.3 M.f. C 10 H 8 N 2 O 2 S Supplementary Entries – Extended norbormide 409 COMMERCIALISATION: History Fungicide introduced by Nippon Kayaku Co., Ltd. PRODUCTS: Discontinued products ‘Styrocide’* (Nippon Kayaku). norbormide Rodenticide NOMENCLATURE: Common name nobormide ((f) F-ISO); norbormide (BSI, E-ISO, ANSI) IUPAC name 5-(α-hydroxy-α-2-pyridylbenzyl)-7-(α-2-pyridylbenzylidene)-8,9,10- trinorborn-5-ene-2,3-dicarboximide Chemical Abstracts name 3a,4,7,7a-tetrahydro-5-(hydroxyphenyl-2-pyridinylmethyl)- 8-(phenyl-2-pyridinylmethylene)-4,7-methano-1H-isoindole-1,3(2H)-dione CAS RN [991–42–4] EC no 213–589–6 Development codes McN-1025 (McNeil) Smiles code OC(C1=CC2C3C(C1C2=C(c4ccccc4)c5ccccn5)C(=O)NC3=O)(c6ccccc6) c7ccccn7 PHYSICAL CHEMISTRY: Composition Mixture of stereoisomers. Mol. wt. 511.6 M.f. C 33 H 25 N 3 O 3 Form Colourless to off-white crystalline powder. M.p. >160 °C Solubility In water 60 mg/l (room temperature). In ethanol 14, chloroform >150, diethyl ether 1, 0.1M hydrochloric acid 29 (all in mg/l, 30 °C). Stability Stable at room temperature when dry, and to boiling water; hydrolysed by alkali. COMMERCIALISATION: History Rodenticide reported by A. P. Roszkowski et al. (Science, 1964, 144, 412). Introduced by the McNeil Laboratories Inc. Patents GB 1059405 APPLICATIONS: Uses A selective rodenticide lethal to all members of the genus Rattus that have been tested. It is relatively non-lethal to other rodents. Formulation types CB . PRODUCTS: Discontinued products ‘Raticate’* (McNeil); ‘Shoxin’* (McNeil). ANALYSIS: Product analysis by uv spectrometry (C. A. Janick et al., J. Pharm. Sci., 1966, 55, 1077). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for Rattus rattus 52, R. norvegicus, R. hawaiiensisc. 10, mice 2250, hamsters 140, prairie dogs >1000 mg/kg; a single oral dose of 1000 mg/kg had no effect on cats, dogs, monkeys, nor was it lethal to any of 40 other animal species tested (P. Roszkowski, J. Pharmacol. Exp. Ther., 1965, 149, 288). NOEL Three adult male 410 The Pesticide Manual Sixteenth Edition © BCPC 2012 noruron volunteers received 15 mg/kg daily for 3 d without ill-effect. Toxicity Class WHO (a.i.) II EC Classifcation Xn; R22 nornicotine Insecticide NOMENCLATURE: Common name nornicotine (traditional name) IUPAC name (S)-3-(pyrrolidin-2-yl)pyridine Chemical Abstracts name (S)-3-(2-pyrrolidinyl)pyridine CAS RN [494–97–3] Smiles code C1CNC(C1)c2cccnc2 PHYSICAL CHEMISTRY: Mol. wt. 148.2 M.f. C 9 H 12 N 2 COMMERCIALISATION: History Insecticide. noruron Herbicide For stereochemistry, see W. R. Diveley et al., J. Org. Chem., 34, 616 (1969). NOMENCLATURE: Common name norea (ANSI, WSSA); noruron (BSI, E-ISO, (m) F-ISO) IUPAC name (3aRS,4SR,5RS,7SR,7aRS)-1,1-dimethyl-3-(perhydro-4,7-methanoinden-5-yl) urea; (3aRS,4SR,5RS,7SR,7aRS)-3-(hexahydro-4,7-methanoindan-5-yl)-1,1-dimethylurea Chemical Abstracts name 3aα,4α,5α,7α,7aα-N,N-dimethyl-N′-(octahydro-4,7-methano- 1H-inden-5-yl)urea CAS RN [18530–56–8] 3aα,4α,5α,7α,7aα- isomer; [2163–79–3] unstated stereochemistry Development codes Hercules 7531 Smiles code CN(C)C(=O)NC1CC2CC1C3CCCC23 PHYSICAL CHEMISTRY: Mol. wt. 222.3 M.f. C 13 H 22 N 2 O COMMERCIALISATION: History Herbicide reported by G. A. Buntin et al. (Abstr. Am. Chem. Soc. Meeting, Los Angeles, 1963). Introduced by Hercules Inc., Agrochemical Div. (and later Nor-Am.). APPLICATIONS: Mode of action Selective herbicide. PRODUCTS: Discontinued products ‘Herban’* (Hercules). Supplementary Entries – Extended nuarimol 411 TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22 nuarimol Fungicide FRAC 3, G1; SBI Class I, DMI: pyrimidine NOMENCLATURE: Common name nuarimol (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name (±)-2-chloro-4′-fuoro-α-(pyrimidin-5-yl)benzhydryl alcohol Chemical Abstracts name (±)-α-(2-chlorophenyl)-α-(4-fuorophenyl)-5- pyrimidinemethanol CAS RN [63284–71–9] unstated stereochemistry EC no 264–071–1 Development codes EL-228 (Lilly) Smiles code OC(c1ccc(F)cc1)(c2cncnc2)c3ccccc3Cl PHYSICAL CHEMISTRY: Mol. wt. 314.7 M.f. C 17 H 12 ClFN 2 O Form Colourless crystals. M.p. 126–127 °C V.p. <0.0027 mPa (25 °C) K ow logP = 3.18 (pH 7) Henry 6.73 × 10 –8 Pa m 3 mol –1 (calc.) S.g./density 0.6–0.8 (bulk) Solubility In water 26 mg/l (pH 7, 25 °C). In acetone 170, methanol 55, xylene 20 (all in g/l, 25 °C). Readily soluble in acetonitrile, benzene, and chloroform. Slightly soluble in hexane. Stability Decomposed rapidly by uv light. Stable at 52 °C. COMMERCIALISATION: History Fungicide introduced in Greece (1980) by Eli Lilly & Co. (agrochemical interests later Dow AgroSciences). Rights sold to Gowan Co. Patents GB 1218623 APPLICATIONS: Biochemistry Sterol demethylation (ergosterol biosynthesis) inhibitor. Mode of action Systemic foliar fungicide with curative and protective action. Interferes with the completion of division of sporids. Uses Control of a wide range of pathogenic fungi, such as Pseudocercosporella spp., Septoria spp., Ustilago spp., powdery mildew, leaf spot, etc., in cereals, both as a foliar spray and as a seed treatment; powdery mildews on pome fruit, stone fruit, vines, hops, cucurbits, and other crops; scab on apples; etc. Formulation types EC; SC. SL; WP; Seed treatment. F C OH N N Cl 412 The Pesticide Manual Sixteenth Edition © BCPC 2012 OCH PRODUCTS: Discontinued products ‘Cidorel’* (BASF Española); ‘Gandural’* (Dow AgroSciences); ‘Gauntlet’* (Shell); ‘Tridal’* (Dow AgroSciences); ‘Trimidal’* (Dow AgroSciences); ‘Triminol’* (DowElanco); Discontinued mixtures ‘Gandural S’* (+ sulfur) (Dow AgroSciences). ANALYSIS: Product analysis by glc with FID (E. W. Day & O. D. Decker, Anal. Methods Pestic. Plant Growth Regul., 1984, 13, 183). Residues in soil and plant tissue determined by glc with ECD (idem, ibid.). Details available from Dow AgroSciences. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, 2004/129/EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 1250, female rats 2500, male mice 2500, female mice 3000, beagle dogs 500 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. No skin irritation; slight eye irritant (rabbits). Not a skin sensitiser (guinea pigs). Inhalation Rats essentially unaffected after 1 h by 0.37 mg tech./l air. NOEL (2 y) for rats and mice 50 mg/kg diet. Toxicity Class WHO (a.i.) III EPA (formulation) III ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 200 mg/kg. Fish LC 50 (96 h) for bluegill sunfshc. 12.1 mg/l. Daphnia LC 50 (48 h) >25 mg/l. Algae EC 50 (96 h) for Selenastrum capricornutum 2.5 mg/l. Bees Not toxic to bees; LC 50 (contact) >11 μg/l. Worms NOEC (14 d) for earthworms 100 g/kg soil. ENVIRONMENTAL FATE: Animals In rats, following oral administration, elimination is rapid. Plants Numerous photodegradation products are formed. Soil/Environment Microbial degradation is accelerated by light; DT 50 (lab.) 344 d, (feld)c. 150 d. K oc 2–6, depending on soil type. OCH Fungicide, herbicide NOMENCLATURE: Common name OCH (WSSA) IUPAC name octachlorocyclohex-2-enone Chemical Abstracts name 2,3,4,4,5,5,6,6-octachloro-2-cyclohexen-1-one CAS RN [4024–81–1] Smiles code ClC1=C(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C1=O PHYSICAL CHEMISTRY: Mol. wt. 371.7 M.f. C 6 Cl 8 O COMMERCIALISATION: History Herbicide and fungicide introduced by Goodrich Chemical Co. Supplementary Entries – Extended 2-(octylthio)ethanol 413 PRODUCTS: Discontinued products ‘Oktone’* (Goodrich). OCS 21693 Herbicide NOMENCLATURE: IUPAC name methyl 2,3,5,6-tetrachloro-N-methoxy-N-methylterephthalamate Chemical Abstracts name methyl 2,3,5,6-tetrachloro-4-[[methoxy(methyl)amino] carbonyl]benzoate CAS RN [14419–01–3] Development codes OCS 21693 Smiles code CON(C)C(=O)c1c(Cl)c(Cl)c(C(=O)OC)c(Cl)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 361.0 M.f. C 11 H 9 Cl 4 NO 4 COMMERCIALISATION: History Herbicidal activity reported by W. Furness (Symp. New Herbic., 3rd, 1969, p. 261). Introduced by Velsicol Corp. (later Sandoz AG). 2-(octylthio)ethanol Insect repellent NOMENCLATURE: IUPAC name 2-(octylthio)ethanol Chemical Abstracts name 2-(octylthio)ethanol Other names 2-hydroxyethyl octyl sulfde CAS RN [3547–33–9] EC no 222–598–4 Development codes Phillips R-874 Smiles code CCCCCCCCSCCO PHYSICAL CHEMISTRY: Mol. wt. 190.3 M.f. C 10 H 22 OS Form Pale amber liquid, with a mild, mercaptan-like odour. M.p. 0 °C B.p. 98 °C /0.1 mmHg V.p. 79 mPa (25 °C) K ow logP = 0.561 S.g./density 0.925–0.935 (24 °C) Solubility Slightly soluble in water; miscible with most organic solvents including refned kerosene, though a co-solvent such as isopropanol is required with the latter to maintain solution at low temperatures. Stability Stable at pH 6–8, and to heat and light. COMMERCIALISATION: History Insect-repelling properties reported by L. D. Goodhue (J. Econ. Entomol., 1960, 53, 805). Introduced by Phillips Petroleum Co. and by the McLaughlin Gormley King Co. Patents US 2863799 (to Phillips Petroleum Co., 1958) Manufacturers MGK APPLICATIONS: Uses Its chief use is as a repellent to Blattodea, at 1 g/m{2}. Also as a repellent using pressurised ‘patio’ foggers against Formicidae, Muscidae and crawling insects. Formulation types EC; OL . CH 3 (CH 2 ) 7 SCH 2 CH 2 OH 414 The Pesticide Manual Sixteenth Edition © BCPC 2012 oxapyrazon; oxapyrazon-sodium; oxapyrazon-(2-hydroxyethyldimethylammonium) ANALYSIS: Details of a glc method available from McLaughlin Gormley King Co. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 8530 mg/kg. Skin and eye Acute percutaneous LD 50 for albino rabbits 13 590 mg/kg. Application of 0.05 mg to the cornea of albino rats produced corneal necrosis in 2 of the 5 eyes tested, but they healed without opacities. Inhalation LC 50 (4 h) for rats 6.12 mg/l. NOEL In 90 d feeding trials, rats receiving 20 000 mg/kg diet showed no adverse effect. Toxicity Class WHO (a.i.) U. EC Classifcation Xi; R41 ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks and bobwhite quail >8000 mg/kg diet. Fish LC 50 (96 h) for rainbow trout 2.9, bluegill sunfsh 2.7 mg/l. Daphnia LC 50 (48 h) 0.38 mg/l. oxapyrazon; oxapyrazon-sodium; oxapyrazon-(2-hydroxyethyldimethylammonium) Herbicide NOMENCLATURE: Common name oxapyrazon* (BSI (1984–1990), E-ISO (pre-1990), for 2-hydroxyethyldimethylammonium salt); oxapyrazone ((f) F-ISO); oxapyrazon (Canada, since 1990 BSI, E-ISO) IUPAC name 5-bromo-1,6-dihydro-6-oxo-1-phenylpyridazin-4-yloxamic acid Chemical Abstracts name [(5-bromo-1,6-dihydro-6-oxo-1-phenyl-4-pyridazinyl) amino]oxoacetic acid CAS RN [4489–31–0] oxapyrazon; [25316–56–7] oxapyrazon-sodium; [25316–57–8] oxapyrazon-(2-hydroxyethyldimethylammonium) Development codes BAS 3380H (oxapyrazon-sodium); BAS 350H (oxapyrazon-(2- hydroxyethyldimethylammonium)) (both BASF) Smiles code oxapyrazon-sodium:[Na+].[O-]C(=O)C(=O)Nc1cnn(c2ccccc2)c(=O)c1Br PHYSICAL CHEMISTRY: Mol. wt. 338.1; (sodium salt 360.1; 2-hydroxyethyldimethylammonium salt 427.3) M.f. C 12 H 8 BrN 3 O 4 ; (sodium salt C 12 H 7 BrN 3 NaO 4 ; 2-hydroxyethyldimethylammonium salt C 16 H 19 BrN 4 O 5 ) COMMERCIALISATION: History Herbicide developed by BASF AG. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Supplementary Entries – Extended oxydeprofos 415 oxathiapiprolin Fungicide NOMENCLATURE: Common name oxathiapiprolin (pa ISO) IUPAC name 1-(4-{4-[(5RS)-5-(2,6-difuorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3- thiazol-2-yl}-1-piperidyl)-2-[5-methyl-3-(trifuoromethyl)-1H-pyrazol-1-yl]ethanone Chemical Abstracts name 1-[4-[4-[5-(2,6-difuorophenyl)-4,5-dihydro-3- isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifuoromethyl)-1H-pyrazol- 1-yl]ethanone CAS RN [1003318–67–9] Development codes DPX–QGU42 Smiles code Cc1cc(nn1CC(=O)N 2 CCC(CC2)c3nc(cs3)C4=NOC(C4)c5c(cccc5F)F)C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 539.52 M.f. C 24 H 22 F 5 N 5 O 2 S oxydeprofos Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name oxydé(profos) ((m) F-ISO); oxydeprofos (BSI, E-ISO); ESP (JMAF) IUPAC name S-2-ethylsulfnyl-1-methylethyl O,O-dimethyl phosphorothioate Chemical Abstracts name S-[2-(ethylsulfnyl)-1-methylethyl] O,O-dimethyl phosphorothioate CAS RN [2674–91–1] Development codes Bayer 23 655; S 410 Smiles code CCS(=O)CC(C)SP(=O)(OC)OC PHYSICAL CHEMISTRY: Mol. wt. 260.3 M.f. C 7 H 17 O 4 PS 2 Form Yellow oil. B.p. 115 °C /0.02 mmHg V.p. 0.625 mPa (20 °C) S.g./density 1.257 (20 °C) Solubility Soluble in water, alcohols, chlorinated hydrocarbons, ketones; sparingly soluble in light petroleum. COMMERCIALISATION: History Insecticide described by G. Schrader (Phosphorsäure-Ester). Introduced by Bayer AG. Patents DE 1035958; US 2952700 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic and contact insecticide and acaricide. Uses Effective against sap-feeding insects and mites at 25 g/100 l. CF 3 S N N O F F N O N N CH 3 416 The Pesticide Manual Sixteenth Edition © BCPC 2012 oxydisulfoton Formulation types EC. PRODUCTS: Discontinued products ‘Estox’* (Bayer); ‘Metasystox S’* (Bayer). ANALYSIS: Product analysis is by titration after reduction by titanium disulfate. Residues may be determined by glc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 105 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats 800 mg/kg. NOEL In 50 d feeding trials, the growth of rats receiving 10 mg/kg daily was not affected. Other I.p. LD 50 for guinea-pigs 100 mg/kg. Toxicity Class WHO (a.i.) Ib ECOTOXICOLOGY: Fish LC 50 (48 h) for carp and Japanese killifsh >40 mg/l. oxydisulfoton Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name oxydisulfoton (BSI, E-ISO, (m) F-ISO) IUPAC name O,O-diethyl S-2-ethylsulfnylethyl phosphorodithioate Chemical Abstracts name O,O-diethyl S-[2-(ethylsulfnyl)ethyl] phosphorodithioate CAS RN [2497–07–6] EC no 219–679–1 Development codes Bayer 23 323; S 309; L 16/184 Smiles code CCOP(=S)(OCC)SCCS(=O)CC PHYSICAL CHEMISTRY: Mol. wt. 290.4 M.f. C 8 H 19 O 3 PS 3 COMMERCIALISATION: History Insecticide and acaricide introduced by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide. PRODUCTS: Discontinued products ‘Disyston S’* (Bayer). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T+; R28| T; R24| N; R50, R53| concn. dep. Supplementary Entries – Extended pebulate 417 parafuron Herbicide NOMENCLATURE: Common name parafuron (BSI, E-ISO, (m) F-ISO) IUPAC name 1,1-dimethyl-3-(α,α,α-trifuoro-p-tolyl)urea Chemical Abstracts name N,N-dimethyl-N′-[4-(trifuoromethyl)phenyl]urea CAS RN [7159–99–1] Development codes C 15 935 Smiles code CN(C)C(=O)Nc1ccc(cc1)C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 232.2 M.f. C 10 H 11 F3N 2 O COMMERCIALISATION: History Herbicide introduced by Ciba AG (later Ciba-Geigy AG). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O pebulate Herbicide HRAC N WSSA 8; thiocarbamate NOMENCLATURE: Common name pebulate (BSI, E-ISO, (m) F-ISO, WSSA, JMAF) IUPAC name S-propyl butyl(ethyl)thiocarbamate Chemical Abstracts name S-propyl butylethylcarbamothioate CAS RN [1114–71–2] EC no 214–215–4 Development codes R-2061 (Stauffer) Smiles code CCCCN(CC)C(=O)SCCC PHYSICAL CHEMISTRY: Composition Tech. material is 95% pure. Mol. wt. 203.3 M.f. C 10 H 21 NOS Form Colourless or yellow liquid, with an aromatic odour. B.p. 142 °C /21 mmHg V.p. 9 Pa (30 °C); 4.7 Pa (25 °C) K ow logP = 3.83 Henry ≤20 Pa m 3 mol –1 (20 °C, calc.) S.g./density 0.956 (20 °C) Solubility In water 60 mg/l (20 °C). Miscible with most organic solvents, e.g. acetone, benzene, toluene, xylene, methanol, isopropanol and kerosene. Stability Stable up to 200 °C. In water, DT 50 (40 °C) 11 d (pH 4 and pH 10), 12 d (pH 7). F.p. 124 °C COMMERCIALISATION: History Herbicide reported by E. O. Burt (Proc. South. Weed Conf., 12th, 1959, p. 19). C N O S CH 3 (CH 2 ) 3 CH 3 CH 2 (CH 2 ) 2 CH 3 418 The Pesticide Manual Sixteenth Edition © BCPC 2012 pebulate Introduced by Stauffer Chemical Co. (now Syngenta AG). Divested to Cedar Chemical Corp. in 2001. Patents US 3175897 APPLICATIONS: Biochemistry Inhibits lipid synthesis (not ACCase inhibition). The sulfoxide may be the active form (P. B. Barrett & J. L. Harwood, Proc. Br. Crop Prot. Conf. – Weeds, 1993, 1, 183). Mode of action Selective systemic herbicide, absorbed by the roots, with translocation throughout the plant. Acts by inhibition of germination. Uses Control of annual grasses (including nutgrasses) and some broad-leaved weeds in sugar beet, tomatoes and tobacco. Applied pre-emergence, at 4–6 kg/ha with soil incorporation. Formulation types EC; GR. PRODUCTS: Discontinued products ‘Tillam’* (Tri-Ag); Discontinued mixtures ‘Edge’* (+ fonofos) (Zeneca). ANALYSIS: Product analysis by glc with FID (AOAC Methods, 18th Ed., 974.05; CIPAC Handbook, 1983, 1B, 1887). Residues in crops and soils determined by glc (G. G. Patchett et al., Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 4, 343; W. Y. Ja et al., Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 698). See also Pestic. Anal. Man., II, 180.238. In soil or water by glc with NPD (AOAC Methods, 18th Ed., 991.07; Environ. Chem. Methods). Analytical methods available from Syngenta. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 76 (1988); a general review of thiocarbamates. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1120, mice 1652 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 4640 mg/kg. Slight irritation of skin, eyes and mucous membranes (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 (4 h) for female rats >3.5 mg/l. NOEL (2 y) for rats 0.74 mg/kg b.w. daily (EPA RED). Not carcinogenic or teratogenic. ADI/RfD (EPA) aRfD 0.5, cRfD 0.007 mg/kg b.w. [1999]. Toxicity Class WHO (a.i.) II EPA (formulation) III EC Classifcation Xn; R22| N; R51, R53 ECOTOXICOLOGY: Birds Dietary LC 50 (7 d) for bobwhite quail 8400 mg/kg diet. Fish LC 50 (96 h) for rainbow trout and bluegill sunfshc. 7.4 mg/l; (48 h) for silver mullet 6.25, killifsh 7.78 mg/l. Daphnia LC 50 (48 h) 5.9 mg/l. Bees Non-toxic to bees at 0.011 mg/bee. ENVIRONMENTAL FATE: Animals In animals, pebulate is rapidly metabolised. In rats, following oral administration,c. 50% was expired as CO 2 , 25% excreted in the urine, and 5% excreted in the faeces, within 3 days. Plants In plants, pebulate is rapidly metabolised to CO 2 and naturally-occurring plant constituents. Soil/Environment In soil, pebulate disappears mainly by microbial degradation to the mercaptan, ethylbutylamine and CO 2 . DT 50 in soil 2–3 w. Supplementary Entries – Extended pentanochlor 419 penfuron Insecticide benzoylurea NOMENCLATURE: IUPAC name 1-(2,6-difuorobenzoyl)-3-(α,α,α-trifuoro-p-tolyl)urea Chemical Abstracts name 2,6-difuoro-N-[[[4-(trifuoromethyl)phenyl]amino]carbonyl] benzamide CAS RN [35367–31–8] Development codes PH-60-44 (Duphar); TH-60-44 (Thompson-Hayward) PHYSICAL CHEMISTRY: Mol. wt. 287.2 M.f. C 15 H 9 F 5 N 2 O 2 COMMERCIALISATION: History Evaluated by Duphar B.V. and Thompson-Hayward Chemical Co.; EUP granted in 1983 (Shibuya). APPLICATIONS: Uses Evaluated against spruce budworm. Effective against pests of stored products, such as Tribolium castaneum and Trogoderma granarium. Formulation types WP. pentanochlor Herbicide HRAC C2 WSSA 7; anilide NOMENCLATURE: Common name pentanochlor (BSI, E-ISO); CMMP (JMAF); pentanochlore ((f) F-ISO); solan (WSSA, Canada, ex ANSI) IUPAC name 3′-chloro-2-methylvalero-p-toluidide Chemical Abstracts name N-(3-chloro-4-methylphenyl)-2-methylpentanamide CAS RN [2307–68–8] Development codes FMC 4512 Smiles code CCCC(C)C(=O)Nc1ccc(C)c(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 239.7 M.f. C 13 H 18 ClNO Form Colourless solid; (tech., colourless to pale cream powder). M.p. 85–86 °C (pure); 82–86 °C (tech.) V.p. Very low at room temperature S.g./density 1.106 (20 °C) Solubility In water 8–9 mg/l (20 °C). In diisobutyl ketone 460, isophorone 550, methyl isobutyl ketone 520, xylene 200–300, pine oil 410 (all in g/kg, 20 °C). Stability Stable to hydrolysis in neutral media at room temperature. CH 3 Cl NHCOCH(CH 2 ) 2 CH 3 CH 3 420 The Pesticide Manual Sixteenth Edition © BCPC 2012 perfuidone COMMERCIALISATION: History Herbicide reported by D. H. Moore (Proc. Northeast. Weed Control Conf., 1960, p. 86). Introduced by FMC Corp. Patents GB 869169; US 3020142 APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective, contact herbicide with absorption via the leaves. Uses Selective pre- and post-emergence herbicidal control in carrots, celeriac, celery, fennel, parsley, and parsnips, at <4 kg/ha. Used pre-sowing on tomatoes and some fower crops, and as a contact spray in carnations, chrysanthemums, fruit trees, ornamental trees and shrubs, roses, sweet peas, and tomatoes. With chlorpropham, used as above, though also on narcissi and tulips. Formulation types EC. PRODUCTS: Discontinued products ‘Croptex Bronze’* (Certis UK); ‘Solan’* (Nufarm UK); Discontinued mixtures ‘Atlas Brown’* (+ chlorpropham) (Nufarm UK). ANALYSIS: Residues determined by hydrolysis to 3-chloro-p-toluidine which is estimated by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >10 000 mg/kg. Skin and eye Slight irritation of skin and mucous membranes. NOEL In 140 d feeding trials, rats receiving 20 000 mg/kg diet suffered no effect on body weight or survival, but histopathological changes were found in the liver; these effects were not observed at 2000 mg/kg diet. Toxicity Class WHO (a.i.) U EPA (formulation) IV ECOTOXICOLOGY: Bees Not very toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Similar to 3,4-dichloroaniline-based acylanilide herbicides; converted to 3-chloro-4-methylaniline. This does not accumulate but is converted to 3,3′-dichloro- 4,4′-dimethylazobenzene. perfuidone Herbicide NOMENCLATURE: Common name perfuidone (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name 1,1,1-trifuoro-N-(4-phenylsulfonyl-o-tolyl)methanesulfonamide; 1,1,1-trifuoro-2′-methyl-4′-(phenylsulfonyl)methanesulfonanilide Chemical Abstracts name 1,1,1-trifuoro-N-[2-methyl-4-(phenylsulfonyl) Supplementary Entries – Extended perfuidone 421 phenyl]methanesulfonamide CAS RN [37924–13–3] EC no 253–718–3 Development codes MBR-8251 Smiles code Cc1cc(ccc1NS(=O)(=O)C(F)(F)F)S(=O)(=O)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 379.4 M.f. C 14 H 12 F 3 NO 4 S 2 Form Colourless crystals. M.p. 142–144 °C V.p. <1.3 mPa (25 °C) Solubility In water 60 mg/l (22 °C). In acetone 750, methanol 595, acetonitrile 560, chloroform 175, dichloromethane 162, diethyl ether 93, benzene 11, hexane 0.03 (all in g/l, 22 °C). Stability Stable to both acid and alkaline hydrolysis, and to heat. Susceptible to slow degradation in aqueous solution under uv irradiation. pKa 2.5 COMMERCIALISATION: History Herbicide reported by W. A. Gentner (Agric. Res. (Wash., D.C.), 1971, 20(2), 5). Introduced by 3M Company. Patents GB 1306564; BE 765558 APPLICATIONS: Biochemistry Interferes with protein biosynthesis and with cellular respiration. Mode of action Selective herbicide which acts by contact and by root absorption. Uses Pre-emergence herbicide for control of Cyperus esculentus, many monocotyledonous weeds, and certain broad-leaved weeds in cotton, transplanted tobacco, rice, sugar cane, and established turf at 1.1–4.5 kg/ha. Phytotoxicity Phytotoxic to carrots, oats, sugar beet, soya beans, and spinach. Formulation types WP; GR; SL . Compatibility Incompatible with liquid nitrogen fertilisers and acidic fertilisers. PRODUCTS: Other mixtures ‘Destun’* (+ benazolin) (3M). ANALYSIS: Product analysis by glc of a derivative with FID (C. D. Green, Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 437). Residues determined by glc of a derivative with ECD (idem, ibid.). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 633, mice 920 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >4000 mg/kg. Severe eye irritant; mild skin irritant (rabbits). Inhalation LC 50 (4 h) for rats 3.2 mg/l air. NOEL In 90 d feeding trials, rats receivingc. 800 mg/kg diet and dogs receivingc. 200 mg/kg showed no ill effects. ADI/RfD (EPA) 0.01 mg/ kg b.w. [1989]. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R22| Xi; R36 ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for quail 7144, ducks >10 000 mg/kg (for WP formulation). Fish LC 50 (96 h) for rainbow trout 312, bluegill sunfsh 318 mg/l. ENVIRONMENTAL FATE: Soil/Environment In wet, neutral or alkaline soils, leaching occurs, particularly in soils 422 The Pesticide Manual Sixteenth Edition © BCPC 2012 PH 60-38 having low clay or organic matter content. Leaching occurs to a much lesser extent in acidic soils. Microbial action accounts for the breakdown of a signifcant portion of perfuidone in the soil, although photodecomposition and volatilisation also occur to some extent. Soil DT 50 c. 1 month. PH 60-38 Insecticide IRAC 15 NOMENCLATURE: IUPAC name 1-(4-chlorophenyl)-3-(2,6-dichlorobenzoyl)urea Chemical Abstracts name 2,6-dichloro-N-[[(4-chlorophenyl)amino]carbonyl]benzamide CAS RN [35409–97–3] Development codes PH 60-38 Smiles code Clc1ccc(NC(=O)NC(=O)c2c(Cl)cccc2Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 343.6 M.f. C 14 H 9 Cl 3 N 2 O 2 COMMERCIALISATION: History Insect growth regulator evaluated by Philips Duphar (later Uniroyal Chemical Co., Inc.). APPLICATIONS: Biochemistry Chitin synthesis inhibitor. Mode of action Insect growth regulator phenisopham Herbicide NOMENCLATURE: Common name phé(nisophame) ((m) F-ISO); phenisopham (BSI, E-ISO) IUPAC name isopropyl 3-[ethyl(phenyl)carbamoyloxy]carbanilate; 3-(isopropoxycarbonylamino)phenyl N-ethylcarbanilate Chemical Abstracts name 3-[[(1-methylethoxy)carbonyl]amino]phenyl ethylphenylcarbamate CAS RN [57375–63–0] Development codes SN 58 132 (Schering) Smiles code CCN(C(=O)Oc1cccc(NC(=O)OC(C)C)c1)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 342.4 M.f. C 19 H 22 N 2 O 4 Form Colourless solid. M.p. 109–110 °C V.p. 6.65 × 10 –4 mPa (25 °C) Henry 7.59 × 10 –5 Pa m 3 mol –1 (calc.) Solubility In water 3 mg/l (25 °C). In dichloromethane 300, ethanol 98, methanol 60, isopropanol 26, toluene 35 (all in g/l, 25 °C). Stability Unstable under alkaline conditions, DT 50 35 d (pH 9), 29 d (pH 12), 2 d (pH 13), 7 h (pH 14). COMMERCIALISATION: History Herbicide reported in Schering AG Tech. Inf. 1977. Introduced by Schering AG. Patents DE 2413933 Supplementary Entries – Extended phenkapton 423 APPLICATIONS: Mode of action Selective and contact herbicide. It acts mainly by contact but there also appears to be some activity through the soil. Uses Mainly used to control broad-leaved weeds in cotton; applied at 1–2 kg/ha. Formulation types EC. PRODUCTS: Discontinued products ‘Diconal’* (Schering); ‘Verdinal’* (Schering). ANALYSIS: Product analysis by tlc. Residues determined by hydrolysis to N-ethylaniline a derivative being measured by glc with ECD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >4000, mice >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >1000 mg/kg. NOEL (90 d) for rats 1 mg/kg daily; (182 d) for dogs 3 mg/kg daily. Toxicity Class WHO (a.i.) U phenkapton Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name phenkapton (BSI, E-ISO, (m) F-ISO); CMP (JMAF) IUPAC name S-2,5-dichlorophenylthiomethyl O,O-diethyl phosphorodithioate Chemical Abstracts name S-[[(2,5-dichlorophenyl)thio]methyl] O,O-diethyl phosphorodithioate CAS RN [2275–14–1] EC no 218–892–7 Development codes G 28 029 Smiles code CCOP(=S)(OCC)SCSc1cc(Cl)ccc1Cl PHYSICAL CHEMISTRY: Mol. wt. 377.3 M.f. C 11 H 15 Cl 2 O 2 PS 3 COMMERCIALISATION: History Insecticide and acaricide introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T; R23/24/25| N; R50, R53 424 The Pesticide Manual Sixteenth Edition © BCPC 2012 phenobenzuron phenmedipham-ethyl Herbicide NOMENCLATURE: Common name phenmé(diphame-é) ((m) F-ISO); phenmedipham-ethyl (BSI, E-ISO) IUPAC name 3-ethoxycarbonylaminophenyl 3-methylcarbanilate; ethyl 3-(3-methylcarbaniloyloxy)carbanilate Chemical Abstracts name 3-[(ethoxycarbonyl)amino]phenyl (3-methylphenyl) carbamate CAS RN [13684–44–1] Development codes SN 38 574 Smiles code CCOC(=O)Nc1cccc(OC(=O)Nc2cccc(C)c2)c1 PHYSICAL CHEMISTRY: Mol. wt. 314.3 M.f. C 17 H 18 N 2 O 4 COMMERCIALISATION: History Superseded ethyl homologue of phenmedipham. Herbicide evaluated by Schering AG. APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. phenobenzuron Herbicide NOMENCLATURE: Common name phenobenzuron (BSI, E-ISO, (m) F-ISO) IUPAC name 1-benzoyl-1-(3,4-dichlorophenyl)-3,3-dimethylurea Chemical Abstracts name N-(3,4-dichlorophenyl)-N-[(dimethylamino)carbonyl] benzamide CAS RN [3134–12–1] Development codes PP 65–25 Smiles code CN(C)C(=O)N(C(=O)c1ccccc1)c2ccc(Cl)c(Cl)c2 PHYSICAL CHEMISTRY: Mol. wt. 337.2 M.f. C 16 H 14 Cl 2 N 2 O 2 COMMERCIALISATION: History Herbicidal activity reported by P. Poignant et al. (Symp. New Herbic., 2nd, 1965, p. 1). Introduced by Pechiney-Progil (later Rhône-Poulenc Agrochimie). PRODUCTS: Discontinued products ‘Benzomarc’* (Rhône-Poulenc). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O Supplementary Entries – Extended phenylmercury chloride 425 2-phenyl-4H-3,1-benzoxazin-4-one Herbicide NOMENCLATURE: IUPAC name 2-phenyl-4H-3,1-benzoxazin-4-one (I) Chemical Abstracts name (I) CAS RN [1022–46–4] Development codes H-170 Smiles code O=c1oc(nc2ccccc12)c3ccccc3 PHYSICAL CHEMISTRY: Mol. wt. 223.2 M.f. C 14 H 9 NO 2 COMMERCIALISATION: History Herbicide reported by A. Fischer (Meded. Landbouwhogesch. Opzoekingsstn. Staat Gent, 1965, 30, 163). Introduced by BASF AG. PRODUCTS: Discontinued products ‘Linurotox’* (BASF). phenylmercury chloride Fungicide NOMENCLATURE: IUPAC name phenylmercury chloride Chemical Abstracts name chlorophenylmercury CAS RN [100–56–1] PHYSICAL CHEMISTRY: Mol. wt. 313.1 M.f. C 6 H 5 ClHg Form Colourless crystals. M.p. 250 °C V.p. 1.3 × 10-2 mPa (0 °C); 1.3 mPa (45 °C) Solubility In water 0.003%. Readily soluble in acetone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, DMF. Slightly soluble in benzene, toluene, xylene, chloroform, methanol, ethanol (room temperature). Sparingly soluble in carbon tetrachloride, diethyl ether, petroleum ether and mineral oils. Stability Stable under neutral conditions. Weak alkalis convert it to phenylmercury hydroxide, strong alkalis to the oxide. Stable in acidic media at room temperature. COMMERCIALISATION: Manufacturers Arco Chemie; Bayer; ICI; Steetley APPLICATIONS: Mode of action Curative fungicide. Uses Dry fungicidal treatment for the protection of seed (wheat, rye, barley, and oats) against Stinking smut, snow mould and barley leaf stripe. Formulation types WP. PRODUCTS: Discontinued products ‘Agronal’* (Spolana); Discontinued mixtures ‘Tillantox’* (+ benquinox) (Bayer). 426 The Pesticide Manual Sixteenth Edition © BCPC 2012 phenylmercury dimethyldithiocarbamate ANALYSIS: Product analysis by titration (AOAC Methods, 18th Ed., 971.04) or gravimetrically (ibid., 973.11). Mercury impurities determined (CIPAC Handbook, 1994, F, 264). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 1 (1976), 86 (1989), both general reviews of mercury and its compounds. JMPR Evaln. 9 (1967). EU Status (1107/2009) Aryl mercury compounds considered to be outside the scope of the Directive; already banned, 79/117/EEC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for highly soluble organic mercury compounds 50–100 mg/kg. Skin and eye Causes irritation of skin, mucous membranes and respiratory organs. ADI/RfD (JMPR) No ADI [1967]. PIC Yes. phenylmercury dimethyldithiocarbamate Fungicide NOMENCLATURE: IUPAC name phenylmercury dimethyldithiocarbamate Chemical Abstracts name (dimethylcarbamodithioato-S,S′)phenylmercury CAS RN [32407–99–1] Smiles code CN(C)C(=S)[S-].[Hg+]c1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 397.9 M.f. C 9 H 11 HgNS 2 Form Fine colourless to grey-white powder. M.p. 175 °C V.p. 1.1 × 10 –1 mPa (35 °C) Solubility In water 6 mg/l (20 °C). In aniline 150, cyclohexanone 50, pyridine 50 (all in g/l); readily soluble in chloroform; sparingly soluble in acetic acid, alcohols, diethyl ether, tetrahydrofuran. Stability Stable at 180 °C and in water at pH ≤12. COMMERCIALISATION: History Fungicide introduced by Berk Chemicals (later Steetley Chemicals Ltd). APPLICATIONS: Mode of action Fungicide with low volatility and high stability. Uses Used to eradicate Venturia spp. on most varieties of apples and pears at 1.5–3.0 g (as mercury)/100 l. Phytotoxicity A few varieties of apple and pear are damaged by mercury compounds. PRODUCTS: Discontinued products ‘Phelam’* (Steetley). ANALYSIS: Mercury impurities determined (CIPAC Handbook, 1994, F, 264). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 9 (1967) EU Status (1107/2009) Aryl mercury compounds considered to be outside the scope of the Directive; already banned, 79/117/EEC. Supplementary Entries – Extended phenylmercury nitrate 427 MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Not specifed, but organic mercury generally is assigned T+; R26/27/28| R33| N; R50, R53 (concentration-dependent) PIC Yes. phenylmercury nitrate Bactericide, fungicide NOMENCLATURE: Common name phenylmercury nitrate (BSI, E-ISO, chemical name, used in lieu of common name, although the material used commercially is the basic nitrate with formula as given); nitrate de phé(nylmercure) (draft F-ISO) IUPAC name phenylmercury hydroxide with phenylmercury nitrate; phenylmercury nitrate (basic) Chemical Abstracts name hydroxy(nitrato)diphenyldimercury CAS RN [8003–05–2] Smiles code O[Hg]c1ccccc1.[O-][N+](=O)O[Hg]c1ccccc1 PHYSICAL CHEMISTRY: Composition See notes under Common name. Tech. has a mercury content of 63.4% m/m. Mol. wt. 634.4 M.f. C 12 H 11 Hg 2 NO 4 Form Colourless powder. M.p. c. 188 °C (decomp.) Solubility In water 600 mg/kg (20 °C). In acetone 5, benzene 3, ethanol 1, methanol 9 (g/kg, 20 °C). COMMERCIALISATION: History Fungicide introduced by Steetley Ltd. APPLICATIONS: Uses Used against Venturia spp. on apples and pears,at 1.5–3.0 g (as mercury)/100 l. Seed dressings, usually combined with an insecticide or another fungicide, are used for cereals, sugar beet, fodder beet and mangolds. Phytotoxicity A few varieties of apple and pear are damaged by mercury compounds. PRODUCTS: Discontinued mixtures ‘Harvesan Plus’* (+ gamma-HCH) (Steetley); ‘Murcicide’* (+ captan) (Steetley). ANALYSIS: Product analysis by titration (AOAC Methods, 18th Ed., 971.04) or gravimetrically (ibid., 973.11). Mercury impurities determined (CIPAC Handbook, 1994, F, 264). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 1 (1976), 86 (1989), both general reviews of mercury and its compounds. EU Status (1107/2009) Aryl mercury compounds considered to be outside the scope of the Directive; already banned, 79/117/EEC. MAMMALIAN TOXICOLOGY: Other I.v. LD 50 for rats 27 mg/kg. Toxicity Class WHO (a.i.) Ib EC Classifcation T; R25, R48/24/25| C; R34| Xi; R37| R44 PIC Yes. 428 The Pesticide Manual Sixteenth Edition © BCPC 2012 phosdiphen phosacetim Rodenticide IRAC 1B NOMENCLATURE: Common name phosacé(time) ((f) F-ISO); phosacetim (BSI, E-ISO) IUPAC name O,O-bis(4-chlorophenyl) N-acetimidoylphosphoramidothioate Chemical Abstracts name O,O-bis(4-chlorophenyl) (1-iminoethyl)phosphoramidothioate CAS RN [4104–14–7] EC no 223–874–7 Development codes Bayer 38 819 Smiles code CC(=N)NP(=S)(Oc1ccc(Cl)cc1)Oc2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 375.2 M.f. C 14 H 13 Cl 2 N 2 O 2 PS COMMERCIALISATION: History Rodenticide reported by V. B. Richens (Pest Control, 1967, 35(9), 28). Introduced by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Gophacide’* (Bayer). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T+; R27/28| N; R50, R53 phosdiphen Fungicide NOMENCLATURE: Common name phosdiphen (JMAF) IUPAC name bis(2,4-dichlorophenyl) ethyl phosphate Chemical Abstracts name bis(2,4-dichlorophenyl) ethyl phosphate CAS RN [36519– 00–3] Development codes MTO-460 (Mitsui Toatsu) Smiles code CCOP(=O) (Oc1ccc(Cl)cc1Cl)Oc2ccc(Cl)cc2Cl PHYSICAL CHEMISTRY: Composition Tech. is 95%. Mol. wt. 416.0 M.f. C 14 H 11 Cl 4 O 4 P Form Pale yellow liquid Cl O Cl P OCH 2 CH 3 O O Cl Cl Supplementary Entries – Extended phosfolan 429 (tech.). B.p. 175 °C /0.2 mmHg (tech.) V.p. 66 mPa (20 °C) (tech.) Henry 3.92 × 10 1 Pa m 3 mol –1 (calc.) S.g./density 1.405 (25 °C, tech.) Solubility In water 0.7 mg/l (20 °C). Soluble in acetone, xylene and hexane. Stability Stable in acidic media, but unstable in alkaline media. Hydrolysis DT 50 (25 °C) 7 d (pH 7), 4 d (pH 9). Thermally stable up to 200 °C. COMMERCIALISATION: History Fungicide reported by M. Hamada et al. (Ann. Phytopathol. Soc. Japan, 1971, 37, 365). Introduced by Hokko Chemical Industry Co., Ltd and Mitsui Toatsu Chemicals Inc. (later Mitsui Chemicals Inc.). Patents JP 634549 (to Hokko) Manufacturers Hokko; Mitsui Toatsu APPLICATIONS: Uses Control of rice blast (Pyricularia oryzae). Formulation types EC. ANALYSIS: Product and residue analysis by glc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 6200, mice 5300 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000, mice 9000–9600 mg/kg. APPLICATIONS: (24 h) of tech. to skin and eyes of rabbits produced no irritation. NOEL (90 d) for rats and mice 200 mg/kg diet; (2 y) for rats and mice 30 mg/kg diet. No reproductive, teratogenic or mutagenic effects observed in rats. Toxicity Class WHO (a.i.) U EPA (formulation) III ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 1.7 mg/l. phosfolan Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name phospholan ((m) F-ISO); phosfolan (BSI, E-ISO) IUPAC name diethyl 1,3-dithiolan-2-ylidenephosphoramidate; 2-(diethoxyphosphinylimino)-1,3-dithiolane Chemical Abstracts name diethyl 1,3-dithiolan-2-ylidenephosphoramidate CAS RN [947–02–4] EC no 213–423–2 Development codes EI 47 031 (Cyanamid) Smiles code CCOP(=O)(OCC)N=C1SCCS1 PHYSICAL CHEMISTRY: Mol. wt. 255.3 M.f. C 7 H 14 NO 3 PS 2 Form Pale yellow solid. M.p. 36.5 °C; (tech., 37–45 °C) B.p. 115–118 °C /0.001 mmHg V.p. 0.031 mPa (20 °C) Solubility In water 650 g/l. Soluble in acetone, benzene, cyclohexane, ethanol, and toluene. 430 The Pesticide Manual Sixteenth Edition © BCPC 2012 phosnichlor Slightly soluble in diethyl ether. Sparingly soluble in hexane. Stability Stable under neutral and slightly acidic conditions but hydrolysed at 2>pH>9. COMMERCIALISATION: History Insecticide introduced by American Cyanamid Co. Patents GB 974138; FR 1327386 APPLICATIONS: Biochemistry Cholinesterase inhibitor Mode of action Systemic insecticide and acaricide with contact and stomach action. Uses Control of lepidopterous larvae (particularly Spodoptera spp.), sucking insects, and mites on cotton, cabbage, onions, tobacco, and other crops. Formulation types EC; GR . PRODUCTS: Discontinued products ‘Cyalane’* (Cyanamid); ‘Cylan’* (Cyanamid); ‘Cyolan’* (Cyanamid); ‘Cyolane’* (Cyanamid). ANALYSIS: Residues determined by glc (N. R. Pasarela & E. J. Orloski, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 231). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986), a general review of organophosphorus insecticides. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 8.9, male mice 12.1 mg/kg. Skin and eye Acute percutaneous LD 50 for male rabbits 23, male guinea pigs 54 mg/kg. NOEL In 90 d feeding trials dogs receiving 1 mg/kg daily showed no clinical symptom. Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R27/28 ENVIRONMENTAL FATE: Plants In plants, phosfolan is metabolised at the nitrogen-phosphorus bond to less toxic, water-soluble compounds. phosnichlor Insecticide IRAC 1B NOMENCLATURE: Common name nichlorfos ((m) France); phosnichlor (BSI, E-ISO, (m) F-ISO) IUPAC name O-4-chloro-3-nitrophenyl O,O-dimethyl phosphorothioate Chemical Abstracts name O-(4-chloro-3-nitrophenyl) O,O-dimethyl phosphorothioate CAS RN [5826–76–6] Smiles code COP(=S)(OC)Oc1ccc(Cl)c(c1)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 297.7 M.f. C 8 H 9 ClNO 5 PS Supplementary Entries – Extended pindone 431 COMMERCIALISATION: History Insecticide evaluated by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Isochlorthion’* (Chemagro). phoxim-methyl Insecticide IRAC 1B NOMENCLATURE: Common name phoxime-mé(thyl) ((f) F-ISO); phoxim-methyl (BSI, E-ISO) IUPAC name O,O-dimethyl α-cyanobenzylideneamino-oxyphosphonothioate; dimethoxyp hosphinothioyloxyimino(phenyl)acetonitrile Chemical Abstracts name 3-methoxy-6-phenyl-2,4-dioxa-5-aza-3-phosphapept-5- ene-7-nitrile 3-sulfde; α-[[(dimethoxyphosphinothioyl)oxy]imino]benzeneacetonitrile CAS RN [14816–16–1] Development codes SRA 7760 Smiles code COP(=S)(OC)ON=C(C#N)c1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 270.2 M.f. C 10 H 11 N 2 O 3 PS COMMERCIALISATION: History Superseded dimethyl analogue of phoxim (q.v.). Insecticide evaluated by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). pindone Rodenticide NOMENCLATURE: Common name no name (Portugal); pival* (former exception, Turkey); pivaldione (France); pindone (BSI, E-ISO, (f) F-ISO) IUPAC name 2-pivaloylindan-1,3-dione O COC(CH 3 ) 3 O 432 The Pesticide Manual Sixteenth Edition © BCPC 2012 piproctanyl bromide Chemical Abstracts name 2-(2,2-dimethyl-1-oxopropyl)-1H-indene-1,3(2H)-dione CAS RN [83–26–1] EC no 201–462–8 Smiles code CC(C)(C)C(=O)C1C(=O)c2ccccc2C1=O PHYSICAL CHEMISTRY: Mol. wt. 230.3 M.f. C 14 H 14 O 3 Form Yellow crystals. M.p. 108.5–110.5 °C V.p. Very low Solubility In water 18 mg/l (25 °C). Soluble in most organic solvents. Readily soluble in aqueous alkalis or ammonia to give bright yellow salts. Stability Very stable. COMMERCIALISATION: History Insecticidal properties reported by L. B. Kilgore et al. (Ind. Eng. Chem., 1942, 34, 494). Introduced by Kilgore Chemical Co. Patents US 2310949 APPLICATIONS: Biochemistry Anticoagulant; inhibits blood coagulation by blocking prothrombin formation. Uses Control of rats and mice, in baits containing 250 mg/kg. Bait shyness does not occur after feeding. Renders cereal bait resistant to insect infestation and fungal infection. Formulation types AB; CB; CP; RB . Compatibility Compatible with other rodenticides. PRODUCTS: Discontinued products ‘Pival’* (Marman, Motomco); ‘Pivalyn’* (sodium salt) (Motomco). ANALYSIS: ANALYSIS: by colorimetry (J. B. La Clair, J. Assoc. Off. Agric. Chem., 1955, 38, 299). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 175 (1995). ICSC.515 (2004). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 280, rabbits 150–170, dogs 75–100 mg/kg. Chronic oral LD 50 for rabbits 0.52, dogs 2.5, sheep >12 mg/kg daily. Other Acute LD 50 by injection for rats isc. 50 mg/kg, but it is more toxic when given in small daily doses of 15–35 mg/kg. Dogs are killed by daily doses of 2.5 mg/kg (J. R. Beauregard et al., J. Agric. Food Chem., 1955, 3, 124; J. P. Saunders et al., ibid., p. 762). Toxicity Class WHO (a.i.) Ib EC Classifcation T; R25, R48/25| N; R50, R53 ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks 250, bobwhite quail 1560 mg/kg. Fish LC 50 (96 h) for bluegill sunfsh 1.6, rainbow trout 0.21 mg/l. piproctanyl bromide Plant growth regulator NOMENCLATURE: Common name piproctanyl (for cation) (BSI, E-ISO, (m) F-ISO) IUPAC name 1-allyl-1-(3,7-dimethyloctyl)piperidinium bromide Supplementary Entries – Extended piproctanyl bromide 433 Chemical Abstracts name 1-(3,7-dimethyloctyl)-1-(2-propenyl)piperidinium bromide CAS RN [56717–11–4] piproctanyl bromide; [69309–47–3] piproctanyl Development codes Ro 06–0761/000 (Dr Maag); ACR-1222 Smiles code [Br-].CC(C)CCCC(C)CC[N+]1(CC=C)CCCCC1 PHYSICAL CHEMISTRY: Mol. wt. 346.4; (piproctanyl 266.5) M.f. piproctanyl bromide C 18 H 36 BrN; piproctanyl C 18 H 36 N Form Pale yellow wax. M.p. 75 °C V.p. <5 × 10 –5 mPa (20 °C) Solubility Very soluble in water. In methanol >2400, ethanol 2100, acetone 1400 (all in g/l). Practically insoluble in hexane and cyclohexane. Stability In aqueous solutions, stable for up to 3 years under normal conditions. Stable to hydrolysis at 50 °C (pH 3 to pH 13). Stable to light, and up to 100 °C. COMMERCIALISATION: History Plant growth regulator reported by G. A. Hüppi et al. (Experientia, 1976, 32, 37). The bromide introduced by Dr R. Maag Ltd. Patents DE 2459129 (to Hoffmann-La Roche) APPLICATIONS: Mode of action Plant growth regulator, absorbed by the leaves and roots, but not readily translocated between shoots. Inhibits elongation of internodes, and shortens and stiffens stems and peduncles. Uses Inhibition of longitudinal growth (to produce more compact and sturdier plants) in ornamentals, especially chrysanthemums, but also azaleas, fuchsias, petunias, and calceolarias. Formulation types SL . PRODUCTS: Discontinued products ‘Alden’* (Dr Maag); ‘Stemtrol’* (Dr Maag). ANALYSIS: Product analysis by reaction with sodium phenylsulfde to form allyl phenyl sulfde which is determined by glc. Residues determined in the same way. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 820–990, mice 182 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 115–240 mg/kg. Non-irritating to skin (guinea pigs) and eyes (rabbits). Inhalation LC 50 for rats 1.5 mg/l air. NOEL In 90 d feeding trials, rats receiving 150 mg/kg daily and dogs receiving 25 mg/kg daily showed no signifcant ill-effects. Toxicity Class WHO (a.i.) III ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks and bobwhite quail >10 000 mg/kg diet. Fish LC 50 (96 h) for rainbow trout 12.7, bluegill sunfsh 62 mg/l. Bees Not toxic to bees. 434 The Pesticide Manual Sixteenth Edition © BCPC 2012 pirimetaphos piprotal Insecticide synergist NOMENCLATURE: Common name piprotal (ESA) IUPAC name 5-[bis[2-(2-butoxyethoxy)ethoxy]methyl]-1,3-benzodioxole (I); 1-bis[2-(2- butoxyethoxy)ethoxy]methyl-3,4-methylenedioxybenzene Chemical Abstracts name (I) CAS RN [5281–13–0] Smiles code CCCCOCCOCCOC(OCCOCCOCCCC)c1ccc2OCOc2c1 PHYSICAL CHEMISTRY: Mol. wt. 456.6 M.f. C 24 H 40 O 8 COMMERCIALISATION: History Synergist for pyrethrum reported by L. O. Hopkins & D. R. Maciver (Pyrethrum Post, 1965, 8(2), 3). Introduced by McLaughlin Gormley King Co. PRODUCTS: Discontinued products ‘Tropital’* (MGK). pirimetaphos Insecticide IRAC 1B NOMENCLATURE: Common name pirimetaphos (BSI, E-ISO, (m) F-ISO); pyrimé(taphos) (France) IUPAC name 2-diethylamino-6-methylpyrimidin-4-yl methyl methylphosphoramidate Chemical Abstracts name 2-(diethylamino)-6-methyl-4-pyrimidinyl methyl methylphosphoramidate CAS RN [31377–69–2] Development codes SAN I 52 135 Smiles code CCN(CC)c1nc(C)cc(OP(=O)(NC)OC)n1 PHYSICAL CHEMISTRY: Mol. wt. 288.3 M.f. C 11 H 21 N 4 O 3 P COMMERCIALISATION: History Insecticide evaluated by Sandoz AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Supplementary Entries – Extended pirimiphos-ethyl 435 pirimiphos-ethyl Insecticide IRAC 1B NOMENCLATURE: Common name pirimiphos-ethyl (BSI, E-ISO, ANSI, BAN, ESA); pyrimiphos-é(thyl) ((m) F-ISO) IUPAC name O,O-diethyl O-2-diethylamino-6-methylpyrimidin-4-yl phosphorothioate Chemical Abstracts name O-[2-(diethylamino)-6-methyl-4-pyrimidinyl] O,O-diethyl phosphorothioate CAS RN [23505–41–1] EC no 245–704–0 Development codes PP211 Smiles code CCOP(=S)(OCC)Oc1cc(C)nc(n1)N(CC)CC PHYSICAL CHEMISTRY: Composition Tech. is 95% pure. Mol. wt. 333.4 M.f. C 13 H 24 N 3 O 3 PS Form Straw- coloured liquid; (tech. is a clear red-brown liquid with a mercaptan-like odour). M.p. 15–18 °C (tech.) B.p. Decomposes abovec. 194 °C V.p. 0.68 mPa (20 °C); 39 mPa (25 °C) K ow logP = 5.0 (unionised) S.g./density 1.14 (20 °C) Solubility In water 2.3 mg/l (pH 7.2). Miscible with most organic solvents. Stability Stable for at least 1 year at room temperature, and for at least 5 days at 80 °C. Hydrolysed by acid and base; DT 50 (25 °C) 52–1200 d (pH range 5.5–8.5), most stable pH 7–8. F.p. >60 °C COMMERCIALISATION: History Superseded diethyl homologue of pirimiphos-methyl (q.v.). Insecticide introduced by ICI Plant Protection Division (later Zeneca Agrochemicals). Patents GB 1019227; GB 1205000 Manufacturers Hunan Haili APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Insecticide with contact and respiratory action. Uses Broad-spectrum control of Diptera and Coleoptera soil pests and some foliar pests on bananas and other fruit, feld crops, ornamentals, turf, vegetables, etc. Also used as a seed treatment, and in compost to control sciarid and phorid fies on mushrooms. Phytotoxicity Phytotoxic at high rates of seed dressing. Formulation types DS; EC; GR; CG. PRODUCTS: Discontinued products ‘Fernex’* (Zeneca); ‘Primicid’* (Zeneca); ‘Solgard’* (Zeneca). ANALYSIS: Product analysis by glc with FID (CIPAC Handbook, 1988, D, 146). Identity also by glc, tlc, i.r. O P(OCH 2 CH 3 ) 2 S N N (CH 3 CH 2 ) 2 N CH 3 436 The Pesticide Manual Sixteenth Edition © BCPC 2012 polychloroterpenes or nmr (CIPAC Handbook, 1994, F, 406). Residues determined by glc with FPD or FTD (D. J. W. Bullock, Anal. Methods Pestic. Plant Growth Regul., 1976, 8, 171). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 140–200, guinea pigs 50–100, cats 25–50 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats 1000–2000 mg/kg. Non-irritating to skin; may cause eye irritation (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 (6 h) for rats >5 ppm (no toxic effects over 3 w). NOEL (90 d) for rats 1.6 mg/kg diet (0.08 mg/kg daily); for dogs 0.2 mg/kg daily. For rats receiving 27 mg/kg diet (1.6 mg/kg daily) and dogs 2 mg/kg daily, the only effect was on the cholinesterase levels. Toxicity Class WHO (a.i.) Ib EPA (formulation) II EC Classifcation T; R25| Xn; R21| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks 2.5, bobwhite quail 10–20 mg/kg. Fish LC 50 (96 h) for common carp 0.22, brown trout 0.02 mg/l. Daphnia LC 50 (48 h) 0.3 μg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 21–70 d (non-sterile, aerobic, o.m. 1.8–6.3%, pH 6.0–7.5). For details of persistence in soil, see D. L. Suett, Pestic. Sci., 1975, 6, 385. polychlorodicyclopentadiene isomers Herbicide, insecticide NOMENCLATURE: IUPAC name polychlorodicyclopentadiene isomers CAS RN [8029–29–6] COMMERCIALISATION: History Insecticide and herbicide introduced by Velsicol Chemical Corp. PRODUCTS: Discontinued products ‘Bandane’* (Velsicol). polychloroterpenes Acaricide, insecticide NOMENCLATURE: IUPAC name heptachloro-2,2-dimethyl-3-methylene-8,9,10-trinorbornane Supplementary Entries – Extended polynactins 437 Chemical Abstracts name chlorinated mixed terpenes Other names terpene polychlorinates CAS RN [8001–50–1] Development codes Compound 3961 PHYSICAL CHEMISTRY: Mol. wt. 379.4 M.f. C 10 H 11 Cl 7 (65% Cl) COMMERCIALISATION: History Insecticidal and acaricidal activity of this reaction mixture described by D. L. Kent et al. (Soap Chem. Spec., 1953, 19(6), 157). Introduced by Goodrich Chemical Co. PRODUCTS: Discontinued products ‘Strobane’* (Goodrich). ANALYSIS: Product analysis by tlc (AOAC Methods 18th Ed., 972.05). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: IARC Monographs Programme on the Evaluation of Carcinogenic Risks (1974) 5. IARC 5 (1974). MAMMALIAN TOXICOLOGY: IARC Class 3 polynactins Acaricide See also The Manual of Biocontrol Agents entry: 2:209 NOMENCLATURE: IUPAC name [1R(1R*,2R*,5R*,7R*,10S*,11S*,14S*,16S*,19R*,20R*,23R*,25R*,28 S*,29S*,32S*,34S*)]-5,14,23,32-tetraethyl-2,11,20,29-tetramethyl-4,13,22,31,37,38,3- 9,40-octaoxapentacyclo[32.2.1.17,10.116,19.125,28]tetracontane-3,12,21,30-tetrone (tetranactin); [1R(1R*,2R*,5R*,7R*,10S*,11S*,14S*,16S*,19R*,20R*,23R*,25R*,28S *,29S*,32S*,34S*)]-5,14,23-triethyl-2,11,20,29,32-pentamethyl-4,13,22,31,37,38,39,- 40-octaoxapentacyclo[32.2.1.17,10.116,19.125,28]tetracontane-3,12,21,30-tetrone (trinactin); [1R(1R*,2R*,5R*,7R*,10S*,11S*,14S*,16S*,19R*,20R*,23R*,25R*,28S*, O CH 3 O O R 4 O O CH 3 O O R 2 O O CH 3 O R 1 O CH 3 O R 3 dinactin: R 1 , R 3 = CH 3 - ; R 2 , R 4 = CH 3 CH 2 - tetranactin: R 1 , R 2 , R 3 , R 4 = CH 3 CH 2 - trinactin: R 1 = CH 3 - ; R 2 , R 3 , R 4 = CH 3 CH 2 - 438 The Pesticide Manual Sixteenth Edition © BCPC 2012 potassium cyanate 29S*,32S*,34S*)]-5,23-diethyl-2,11,14,20,29,32-hexamethyl-4,13,22,31,37,38,39,40- -octaoxapentacyclo[32.2.1.17,10.116,19.125,28]tetracontane-3,12,21,30-tetrone (dinactin) Chemical Abstracts name [1R(1R*,2R*,5R*,7R*,10S*,11S*,14S*,16S*,19R*,20R*,23R*,2 5R*,28S*,29S*,32S*,34S*)]-5,14,23,32-tetraethyl-2,11,20,29-tetramethyl-4,13,22,31,37,38,3- 9,40-octaoxapentacyclo[32.2.1.17,10.116,19.125,28]tetracontane-3,12,21,30-tetrone (tetranactin) Other names tetranactin; trinactin; dinactin CAS RN [33956–61–5] tetranactin; [7561–71–9] trinactin; [20261–85–2] dinactin; [39285–04–6] polynactin, formerly [56485–45–1] and [56573–63–8] Smiles code tetranactin, without stereochemistry:CCC1CC2CCC(O 2 )C(C)C(=O)OC(CC)CC3CCC(O3)C(C)C(=O) OC(CC)CC4CCC(O4)C(C)C(=O)OC(CC)CC5CCC(O5)C(C)C(=O)O1 PHYSICAL CHEMISTRY: Composition A mixture of tetranactin, trinactin and dinactin. Mol. wt. 793.1 (tetranactin); 779.0 (trinactin); 765.0 (dinactin) M.f. C 44 H 72 O 12 (tetranactin); C 43 H 70 O 12 (trinactin); C 42 H 68 O 12 (dinactin) M.p. 111–112 °C Solubility In water 0.02 g/l (25 °C). In acetone 56, methanol 17, benzene 387, xylene 243, hexane 8 (all in g/l, 25 °C). COMMERCIALISATION: Production By fermentation of Streptomyces aureus S-3466. APPLICATIONS: Biochemistry Thought to act through leakage of cations through the lipid layer of the mitochondrial membrane. Uses For control of spider mites in fruit trees. Formulation types EC. PRODUCTS: Discontinued mixtures ‘Mitecidin’* (+ fenobucarb) (Eiko Kasei); ‘Mitedown’* (+ fenbutatin oxide) (Eiko Kasei). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice >15 000 mg/kg. Skin and eye Acute percutaneous LD 50 for mice >10 000 mg/kg. Mild skin and eye irritant. Toxicity Class EPA (formulation) IV ECOTOXICOLOGY: Fish TLm for carp 0.003 ppm. potassium cyanate Herbicide NOMENCLATURE: IUPAC name potassium cyanate (I) Chemical Abstracts name (I) CAS RN [590–28–3] EC no 209–676–3 Smiles code [K+].[O-]C#N PHYSICAL CHEMISTRY: Mol. wt. 81.12 M.f. CKNO Form Colourless crystals. S.g./density 2.056 (20 °C) Solubility In water 630 g/l (10 °C), 720 g/l (70 °C). Supplementary Entries – Extended potassium phosphates 439 Stability Slowly hydrolysed in aqueous solution to form ammonia and potassium bicarbonate. COMMERCIALISATION: History Introduced as herbicide by American Cyanamid Co. APPLICATIONS: Mode of action Total herbicide. Formulation types SP. PRODUCTS: Discontinued products ‘Aerocyanate’* (Cyanamid). ANALYSIS: Product analysis by conversion to an insoluble derivative which is weighed (CIPAC Handbook, 1985, 1C, 2200; AOAC Methods, 18th Ed., 952.01). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22 potassium phosphates Fungicide NOMENCLATURE: Chemical Abstracts name monopotassium phosphate Other names potassium dihydrogen phosphate; potassium monophosphate; dipotassium phosphate; dipotassium hydrogen phosphate CAS RN [7778–77–0] monopotassium salt; [7758–11–4] dipotassium salt PHYSICAL CHEMISTRY: Mol. wt. 136.1 (monopotassium salt); 174.2 (dipotassium salt) M.f. H 2 KO 4 P; HK 2 O 4 P Form Crystalline powder. M.p. >465 °C (dipotassium salt) Solubility In water 150 g/100 g. (dipotassium salt) COMMERCIALISATION: History The dipotassium salt was frst registered in USA in 2002. Manufacturers Lidochem APPLICATIONS: Mode of action The dipotassium salt may act both by direct toxicity to the pathogen and also, through its fertiliser action, by stimulating the plant’s natural defences. Uses The monopotassium salt is for control of powdery mildew in fruit and vegetables. Also used as a fertiliser, and as a buffering agent in pesticide formulations. The dipotassium salt is for control of powdery mildews, Downy mildews, leaf spot, root rot, etc in woody ornamentals, turf, grapes, and fruit and nut trees which are not yet bearing. PRODUCTS: Other products ‘Nutrol’ (dihydrogen phosphate) (Lidochem); Discontinued products ‘eKsPunge’* (dihydrogen phosphate) (Lidochem). 440 The Pesticide Manual Sixteenth Edition © BCPC 2012 proclonol TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.608 (potassium dihydrogen phosphate; 2005). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats >5000, female rats >500 mg/kg (dihydrogen phosphate). Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Not a skin irritant; a mild eye irritant (dihydrogen phosphate). primidophos Insecticide IRAC 1B NOMENCLATURE: Common name prymidophos ((m) France); primidophos (BSI, E-ISO, (m) F-ISO) IUPAC name O,O-diethyl O-(2-N-ethylacetamido-6-methylpyrimidin-4-yl) phosphorothioate; N-(4-diethoxyphosphinothioyloxy-6-methylpyrimidin-2-yl)-N- ethylacetamide Chemical Abstracts name O-[2-(acetylethylamino)-6-methyl-4-pyrimidinyl] O,O- diethyl phosphorothioate CAS RN [39247–96–6] Development codes PP484 Smiles code CCOP(=S)(OCC)Oc1cc(C)nc(n1)N(CC)C(=O)C PHYSICAL CHEMISTRY: Mol. wt. 347.4 M.f. C 13 H 22 N 3 O 4 PS COMMERCIALISATION: History Insecticide evaluated by ICI Plant Protection Division (later ICI Agrochemicals). APPLICATIONS: Biochemistry Cholinesterase inhibitor. proclonol Acaricide NOMENCLATURE: Common name proclonol (BAN, JMAF) IUPAC name 4,4′-dichloro-α-cyclopropylbenzhydrol Chemical Abstracts name 4-chloro-α-(4-chlorophenyl)-α-cyclopropylbenzenemethanol CAS RN [14088–71–2] Development codes R-8284 (Janssen) Smiles code OC(C1CC1)(c2ccc(Cl)cc2)c3ccc(Cl)cc3 PHYSICAL CHEMISTRY: Mol. wt. 293.2 M.f. C 16 H 14 Cl 2 O Supplementary Entries – Extended profuazol 441 COMMERCIALISATION: History Acaricide introduced by Janssen Pharmaceutica, N.V. PRODUCTS: Discontinued products ‘Kilacar’* (Asepta). procyazine Herbicide NOMENCLATURE: Common name procyazine (BSI, E-ISO, (f) F-ISO, ANSI) IUPAC name 2-(4-chloro-6-cyclopropylamino-1,3,5-triazin-2-ylamino)-2- methylpropiononitrile Chemical Abstracts name 2-[[4-chloro-6-(cyclopropylamino)-1,3,5-triazin-2-yl]amino]- 2-methylpropanenitrile CAS RN [32889–48–8] Development codes CGA 18 762 Smiles code CC(C)(Nc1nc(Cl)nc(NC2CC2)n1)C#N PHYSICAL CHEMISTRY: Mol. wt. 252.7 M.f. C 10 H 13 ClN 6 COMMERCIALISATION: History Herbicide introduced by Ciba-Geigy AG. ANALYSIS: See Pestic. Anal. Man., I, 302. profuazol Herbicide HRAC E WSSA 14 NOMENCLATURE: Common name profuazol (BSI, E-ISO, (m) F-ISO) IUPAC name 1,2′-dichloro-4′-fuoro-5′-[(6S,7aR)-6-fuoro-2,3,5,6,7,7a-hexahydro-1,3- dioxo-1H-pyrrolo[1,2-c]imidazol-2-yl]methanesulfonanilide Chemical Abstracts name 1-chloro-N-[2-chloro-4-fuoro-5-[(6S,7aR)- 6-fuorotetrahydro-1,3-dioxo-1H-pyrrolo[1,2-c]imidazol-2(3H)-yl]phenyl] methanesulfonamide CAS RN [190314–43–3] Development codes IN-TY029; DPX- TY029 (DuPont) PHYSICAL CHEMISTRY: Mol. wt. 414.2 M.f. C 13 H 11 Cl 2 F 2 N 3 O 4 S COMMERCIALISATION: History Herbicide developed by E. I. du Pont de Nemours & Co. 442 The Pesticide Manual Sixteenth Edition © BCPC 2012 profuralin APPLICATIONS: Biochemistry Inhibitor of protoporphyrinogen oxidase. profuralin Herbicide NOMENCLATURE: Common name profuralin (BSI, E-ISO, ANSI, WSSA); profuraline ((f) F-ISO) IUPAC name N-(cyclopropylmethyl)-α,α,α-trifuoro-2,6-dinitro-N-propyl-p-toluidine; N-cyclopropylmethyl-2,6-dinitro-N-propyl-4-trifuoromethylaniline Chemical Abstracts name N-(cyclopropylmethyl)-2,6-dinitro-N-propyl-4- (trifuoromethyl)benzenamine CAS RN [26399–36–0] EC no 247–656–6 Development codes CGA 10 832 Smiles code CCCN(CC1CC1)c2c(cc(cc2[N+](=O)[O-])C(F)(F)F)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 347.3 M.f. C 14 H 16 F 3 N 3 O 4 Form Yellow-orange crystals. M.p. 32.1–32.5 °C V.p. 8.4 mPa (20 °C) Henry 2.92 × 101 Pa m 3 mol –1 (calc.) S.g./density 1.38 (20 °C) Solubility In water 0.1 mg/l (20 °C). In n-octanol 220 g/l (20 °C); readily soluble in most organic solvents, e.g. ethanol, acetone, xylene, and n-hexane. Stability Stable for at least 3 years under normal storage conditions. Solutions are slowly hydrolysed at 100 °C; DT 50 6 h (pH 3, pH 7 and pH 10). Decomposed by uv light. Decomposes atc. 180 °C. COMMERCIALISATION: History Herbicide reported by T. D. Taylor et al. (Annu. Meet. Weed Sci. Soc. Am., 1973, Abstr. 169). Introduced by Ciba-Geigy AG. Patents US 3546295 APPLICATIONS: Mode of action Selective herbicide, absorbed by the roots and shoots. Uses Control of annual and perennial broad-leaved and grass weeds in cotton, soya beans, brassicas, capsicums, tomatoes, and other crops. Applied pre-planting by soil incorporation at 0.75–1.5 kg/ha. Phytotoxicity Small grains, sorghum, maize, beet and direct-seeded tomatoes are sensitive. Formulation types EC. PRODUCTS: Discontinued products ‘Pregard’* (Ciba-Geigy); ‘Tolban’* (Ciba-Geigy). ANALYSIS: Product analysis by glc with FID (R. A. Kahrs, Anal. Methods Pestic. Plant Growth Regul., 1978, 10, 451). Residues determined by glc with ECD or MCD (idem, ibid.). F 3 C NO 2 NO 2 N CH 2 CH 2 CH 2 CH 3 Supplementary Entries – Extended proglinazine-ethyl; proglinazine 443 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for ratsc. 10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >4000, rats >3170 mg/kg. Non-irritating to skin; moderate eye irritant (rabbits). Inhalation LC 50 (4 h) for rats >3.97 mg/l air. NOEL (90 d) for rats 200 mg/kg diet (c. 13 mg/kg daily); for dogs 600 mg/kg diet (c. 20 mg/kg daily). Toxicity Class WHO (a.i.) U EC Classifcation Xi; R36| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail and mallard ducks 1000 mg/kg. Fish LC 50 (96 h) for bluegill sunfsh 0.023, trout 0.015 mg/l. Bees Toxic to honeybees. ENVIRONMENTAL FATE: Animals For details of metabolites see A. R. Jacobson and J. T. Gerig (Chem Res. Toxicol. 1988, 1, 304). Plants Minute quantities of polar metabolites are produced in cotton and soya beans. Soil/Environment Degraded by soil micro-organisms. No signifcant leaching through the soil. proglinazine-ethyl; proglinazine Herbicide NOMENCLATURE: Common name proglinazine (for the acid) (BSI, E-ISO, (f) F-ISO, WSSA) IUPAC name N-(4-chloro-6-isopropylamino-1,3,5-triazin-2-yl)glycine (for the acid) Chemical Abstracts name N-[4-chloro-6-[(1-methylethyl)amino]-1,3,5-triazin- 2-yl]glycine (for the acid) CAS RN [68228–18–2] ester; [68228–20–6] acid Development codes MG-07 (acid) (Nitrokémia) PHYSICAL CHEMISTRY: Composition Tech. isc. 94%. Mol. wt. 273.3 (ester); 245.7 (acid) M.f. ester C 10 H 16 ClN 5 O 2 ; acid C 8 H 12 ClN 5 O 2 Form Colourless crystals (ester). M.p. 110–112 °C (ester) V.p. 0.27 mPa (20 °C) (ester) Solubility In water 750 mg/l (25 °C, ester). In acetone 500, hexane 35, xylene 100 (all in g/l, 25 °C, ester). Stability Decomposes at 160 °C; stable to light. Stable at room temperature (pH 5–8), but on heating is hydrolysed by acid or alkali to the corresponding herbicidally-inactive hydroxytriazine. COMMERCIALISATION: History The ethyl ester introduced as a herbicide by Nitrokémia Ipartelepek. N N N Cl NHCH 2 CO 2 H (CH 3 ) 2 CHNH 444 The Pesticide Manual Sixteenth Edition © BCPC 2012 promacyl APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Mode of action Selective herbicide. Uses Pre-emergence control of seedling weeds (particularly broad-leaved) in maize at 4 kg/ha. Formulation types WP ANALYSIS: Product analysis by glc. Residues determined by glc with TID. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >8000, rabbits >3000, guinea pigs 857–923 mg/ kg. Skin and eye Acute percutaneous LD 50 for rabbits >4000, rats >1500 mg/kg. Non- irritating to skin and eyes (rabbits). Moderate skin sensitisation (guinea pigs). Other Acute i.p. LD 50 for rats 829–891, mice 720–1080 mg/kg. Toxicity Class WHO (a.i.) U ENVIRONMENTAL FATE: Soil/Environment Degraded in soil, DT 50 56–70 d. promacyl Insecticide, ixodicide IRAC 1A NOMENCLATURE: Common name promacyl (Australia) IUPAC name 5-methyl-m-cumenyl butyryl(methyl)carbamate Chemical Abstracts name 3-methyl-5-(1-methylethyl)phenyl methyl(1- oxobutyl)carbamate Other names promecarb A CAS RN [34264–24–9] Development codes CRC 7320 Smiles code CCCC(=O)N(C)C(=O)Oc1cc(C)cc(c1)C(C)C PHYSICAL CHEMISTRY: Mol. wt. 277.4 M.f. C 16 H 23 NO 3 Form Tech. is a clear amber to dark brown liquid. B.p. 158 °C /5 mmHg V.p. 400 Pa (149 °C) S.g./density 0.996 (20 °C) Solubility Sparingly soluble in water. Miscible with aliphatic and aromatic hydrocarbons, alcohols, esters, ethers, ketones. Stability Stable ≤200 °C; also unchanged after 300 d at 50 °C. COMMERCIALISATION: History Insecticide and ixodicide introduced by ICI Australia (later Crop Care Australasia Pty Ltd). Patents AU 441004; AU 454280 OCONCOCH 2 CH 2 CH 3 CH 3 CH(CH 3 ) 2 CH 3 Supplementary Entries – Extended promecarb 445 APPLICATIONS: Biochemistry Cholinesterase inhibitor Uses Effective for controlling Boophilus microplus on cattle by sprays or plunge dips. Also controls Haemaphysalis longicornis, Haematobia irritans exigua and Ixodes holocyclus on cattle and horses. Formulation types EC. PRODUCTS: Discontinued products ‘Promicide’* (ICI Australia). ANALYSIS: Product analysis by glc (D. Gunew, Anal. Methods Pestic. Plant Growth Regul., 1980, 11, 139). Residues in cattle determined by glc (D. E. Clegg & P. R. Martin, Pestic. Sci., 1973, 4, 447). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for female rats 1220, female mice 2000–4000, female guinea pigs 250, female rabbits 8000 mg/kg. Skin and eye Acute percutaneous LD 50 for female rats >4000 mg/kg. Slight irritant to skin (rats). Inhalation No toxic sign in rats exposed to saturated atmosphere for 6 h/d each 5 d/w for 3 w. NOEL (2 y) for rats 500 mg/kg diet. Toxicity Class WHO (a.i.) II ECOTOXICOLOGY: Birds Acute oral LD 50 for hens 4000–8000 mg/kg. promecarb Insecticide IRAC 1A NOMENCLATURE: Common name promecarb (BSI, E-ISO, ESA, JMAF); promé(carbe) ((m) F-ISO) IUPAC name 5-methyl m-cumenyl methylcarbamate; 3-isopropyl-5-methylphenyl methylcarbamate Chemical Abstracts name 3-methyl-5-(1-methylethyl)phenyl methylcarbamate CAS RN [2631–37–0] EC no 220–113–0 Development codes SN 34 615; SSI 0792 Smiles code CNC(=O)Oc1cc(C)cc(c1)C(C)C PHYSICAL CHEMISTRY: Composition Tech. is >97%. Mol. wt. 207.3 M.f. C 12 H 17 NO 2 Form Colourless crystals. CH 3 CH(CH 3 ) 2 OCONHCH 3 446 The Pesticide Manual Sixteenth Edition © BCPC 2012 promecarb M.p. 87–87.5 °C B.p. 117 °C /0.01 mmHg V.p. 1.4 mPa (25 °C) K ow logP = 3.189 (pH 4) Henry 3.19 × 10 –3 Pa m 3 mol –1 (calc.) Solubility In water 91 mg/l (pH 4–5, 25 °C). Readily soluble in organic solvents, e.g. in acetone, DMF, dichloroethane 400–600, cyclohexanol, cyclohexanone, isopropanol, isobutanol, methanol 200–400, carbon tetrachloride, xylene 100–200 (all in g/l, 25 °C). Stability Hydrolysed by strong acids and alkalis, DT 50 (22 °C) 103 d (pH 7), 36 h (pH 9), stable at pH 5. Stable ≥250 °C, and >140 h at 50 °C. COMMERCIALISATION: History Insecticide reported by A. Formigoni & G. P. Bellini (Congr. Int. Antiparassitari, Naples, 1965) and by A. Jäger (Z. Angew. Entomol., 1966, 58, 188). Introduced by Schering AG (later AgrEvo GmbH). Patents DE 1156272 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide with contact and stomach action; has good initial knockdown of insects. Uses Control of sucking and chewing insects (Colorado Beetles and other Coleoptera, aphids, Lepidoptera larvae, leaf miners, etc.) in potatoes, maize, pome fruit, stone fruit, and citrus fruit. Formulation types EC; WP. Compatibility Incompatible with alkaline materials. PRODUCTS: Discontinued products ‘Carbamult’* (AgrEvo). ANALYSIS: Product analysis by hplc Residues determined by glc with ECD of a derivative. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 60–140, mice 23–40 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2025 mg/kg; (50% WP formulation) for rats and rabbits >1000 mg/kg. Inhalation LC 50 (4 h) for rats >0.16 mg/l air. NOEL (1.5 y) for rats >20 mg/ kg. Toxicity Class WHO (a.i.) II EPA (formulation) II EC Classifcation T; R25| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 78, mallard ducks 3.5 mg/kg. Fish LC 50 (96 h) for rainbow trout 0.3, bluegill sunfsh 0.64 mg/l; (72 h) for carp 4.3 mg/l; (120 h) for European trout 1.2 mg/l. Bees Toxic to bees; LD 50 0.0011 mg/bee. ENVIRONMENTAL FATE: Animals In mammals, the substituted phenol moiety is eliminated after condensation with glucuronic acid. Metabolism of carbamate insecticides is reviewed (M. Cool & C. K. Jankowski in Insecticides). Soil/Environment Presumably, as for other carbamates, cleavage of the N-methylcarbamate moiety and decomposition into CO 2 and methylamine. Soil DT 50 <28 d (lab. and feld studies). Soil adsorption Kd 1.72 (2.64% o.c., pH 6.0), 1.63 (1.01% o.c., pH 6.7). Supplementary Entries – Extended propaphos 447 propaphos Insecticide IRAC 1B NOMENCLATURE: Common name propaphos (BSI, JMAF, E-ISO); propafos ((m) F-ISO) IUPAC name 4-(methylthio)phenyl dipropyl phosphate Chemical Abstracts name 4-(methylthio)phenyl dipropyl phosphate Other names DPMP CAS RN [7292–16–2] Development codes NK-1158 (Nippon Kayaku) Smiles code CCCOP(=O)(OCCC)Oc1ccc(SC)cc1 PHYSICAL CHEMISTRY: Mol. wt. 304.3 M.f. C 13 H 21 O 4 PS Form Colourless liquid. B.p. 175–177 °C /0.85 mmHg V.p. 0.12 mPa (25 °C) K ow logP = 3.67 Henry 2.92 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.1504 (20 °C) Solubility In water 125 mg/l (25 °C). Soluble in most organic solvents. Stability Stable <230 °C; stable in neutral and acidic media, but is slowly decomposed in alkaline media. COMMERCIALISATION: History Insecticide reported (Jpn. Pestic. Inf., 1970, No. 4, p. 7). Introduced by Nippon Kayaku Co., Ltd and frst marketed in Japan in 1973. Patents JP 482500; JP 462729 Manufacturers Nippon Kayaku APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide with contact and stomach action. Uses Control of Chilo suppressalis, Laodelphax striatella, Nephotettix cincticeps, Oulema oryzae (including strains resistant to other organophosphorus and carbamate insecticides) in paddy rice. Applied at 3–5 g/rice nursery tray. Formulation types DP; GR . PRODUCTS: Discontinued products ‘Kayaphos’* (Nippon Kayaku); Discontinued mixtures ‘Fuji- One Kayaphos Oncol’* (+ benfuracarb + isoprothiolane) (Nihon Nohyaku). ANALYSIS: Product and residue analysis by glc (S. Asaka et al., Noyaku Kagayu, 1975, 3, 36). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. J. Pestic. Sci., 1989, 14, 511–515. EU Status (1107/2009) Never notifed to the EU. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 70, mice 90, rabbits 82.5 mg/kg. Skin and eye Acute O P(OCH 2 CH 2 CH 3 ) 2 O CH 3 S 448 The Pesticide Manual Sixteenth Edition © BCPC 2012 propyl 3-tert-butylphenoxyacetate percutaneous LD 50 for rats 88.5 mg/kg. Inhalation LC 50 for rats 39.2 mg/m 3 . NOEL (2 y) for rats 0.08, mice 0.05 mg/kg b.w. Toxicity Class WHO (a.i.) Ib ECOTOXICOLOGY: Birds LD 50 for chickens 2.5–5.0 mg/kg. Fish LC 50 (48 h) for carp 4.8 mg/l. Daphnia Toxic. Bees Toxic to bees. ENVIRONMENTAL FATE: Plants For metabolism in plants, see Y. Fujii et al., J. Pestic. Sci., 1980, 5(1), 55–62. propyl 3-tert-butylphenoxyacetate Plant growth regulator NOMENCLATURE: IUPAC name propyl 3-tert-butylphenoxyacetate Chemical Abstracts name propyl [3-(1,1-dimethylethyl)phenoxy]acetate CAS RN [66227–09–6] Development codes M&B 25 105 Smiles code CCCOC(=O)COc1cccc(c1)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 250.3 M.f. C 15 H 22 O 3 Form Colourless liquid with a characteristic odour. B.p. 162 °C /20 mmHg Solubility Sparingly soluble in water. COMMERCIALISATION: History Plant growth-regulating properties reported by C. J. Hibbitt & J. A. Hardisty (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1979, 44, 835). Introduced by May & Baker Ltd (later Rhône-Poulenc Agrochimie). Patents GB 1524320 APPLICATIONS: Uses Promotes lateral branching in maiden and young non-cropping apple and pear trees by temporarily inhibiting the growth of the apical meristem. Formulation types EC. PRODUCTS: Discontinued products ‘M&B 25105’* (Hortichem). ANALYSIS: Product and residue analysis by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1800 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Moderate irritant to skin and eyes (rabbits). Supplementary Entries – Extended prothidathion 449 propyl isome Insecticide synergist NOMENCLATURE: Common name propyl isome (ESA) IUPAC name dipropyl 5,6,7,8-tetrahydro-7-methylnaphtho[2,3-d]-1,3-dioxole-5,6- dicarboxylate (I); dipropyl 1,2,3,4-tetrahydro-3-methyl-6,7-methylenedioxynaphthalene-1,2- dicarboxylate Chemical Abstracts name (I) Other names dipropyl maleate isosafrole condensate CAS RN [83–59–0] Smiles code CCCOC(=O)C1C(C)Cc2cc3OCOc3cc2C1C(=O) OCCC PHYSICAL CHEMISTRY: Mol. wt. 362.4 M.f. C 20 H 26 O 6 COMMERCIALISATION: History Synergist for pyrethrum reported by M. E. Synerholm & A. Hartzell (Contr. Boyce Thompson Inst., 1945, 14, 79). Introduced by S. B. Penick & Co. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation T; R24| Xn; R22| N; R50, R53 prosulfalin Herbicide NOMENCLATURE: Common name prosulfaline ((m) F-ISO); prosulfalin (BSI, E-ISO, ANSI, WSSA) IUPAC name N-(4-dipropylamino-3,5-dinitrophenylsulfonyl)-S,S-dimethylsulfmide Chemical Abstracts name N-[[4-(dipropylamino)-3,5-dinitrophenyl]sulfonyl]-S,S- dimethylsulflimine CAS RN [51528–03–1] Smiles code CCCN(CCC)c1c(cc(cc1[N+](=O)[O-])S(=O)(=O)N=S(C)C)[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 406.5 M.f. C 14 H 22 N 4 O 6 S 2 COMMERCIALISATION: History Herbicide evaluated by Eli Lilly & Co. prothidathion Acaricide IRAC 1B NOMENCLATURE: Common name prothidathion (BSI, E-ISO, (m) F-ISO) IUPAC name S-2,3-dihydro-5-isopropoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl O,O-diethyl 450 The Pesticide Manual Sixteenth Edition © BCPC 2012 prothiocarb; prothiocarb hydrochloride phosphorodithioate; 3-diethoxyphosphinothioylthiomethyl-5-isopropoxy-1,3,4-thiadiazol- 2(3H)-one Chemical Abstracts name O,O-diethyl S-[[5-(1-methylethoxy)-2-oxo-1,3,4-thiadiazol- 3(2H)-yl]methyl] phosphorodithioate CAS RN [20276–83–9] Development codes GS 13 010 Smiles code CCOP(=S)(OCC)SCn1nc(OC(C)C)sc1=O PHYSICAL CHEMISTRY: Mol. wt. 358.4 M.f. C 10 H 19 N 2 O 4 PS 3 COMMERCIALISATION: History Acaricide evaluated by J. R. Geigy S.A. (later Ciba-Geigy AG). APPLICATIONS: Biochemistry Cholinesterase inhibitor. prothiocarb; prothiocarb hydrochloride Fungicide FRAC 28, F4; carbamate fungicide NOMENCLATURE: Common name prothiocarbe ((m) F-ISO); prothiocarb (BSI, E-ISO) IUPAC name S-ethyl (3-dimethylaminopropyl)thiocarbamate Chemical Abstracts name S-ethyl [3-(dimethylamino)propyl]carbamothioate CAS RN [19622–08–3] prothiocarb; [19622–19–6] hydrochloride EC no 243–193–9 hydrochloride Development codes SN 41 703 (Schering) PHYSICAL CHEMISTRY: Composition Tech. is 95%. Mol. wt. 190.3; (hydrochloride 226.8) M.f. C 8 H 18 N 2 OS; (hydrochloride C8H19ClN 2 OS) Form Prothiocarb hydrochloride is a hygroscopic, colourless, odourless crystalline solid; (tech. has a strong odour). M.p. 120–121 °C (hydrochloride) V.p. 0.0019 mPa (25 °C, hydrochloride) Henry hydrochloride: 4 × 10 –1 0 Pa m 3 mol –1 (calc.) Solubility Hydrochloride: In water 890 g/l (23 °C). In benzene, hexane <0.15, chloroform 100, methanol 680 (all in g/l, 23 °C). COMMERCIALISATION: History Fungicide reported by M. G. Bastiaansen et al. (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1974, 39, 1019). The hydrochloride introduced by Schering AG. Patents DE 1567169. APPLICATIONS: Biochemistry Proposed mode of action is affecting cell membrane permeability, by inhibiting fatty acid biosynthesis. Mode of action Systemic fungicide, taken up by the roots and translocated to the aerial parts. Uses Prothiocarb hydrochloride is a soil-applied fungicide with a specifc action against Phycomycetes, e.g. Phytophthora, Pythium spp. It was only recommended for ornamental crops, mainly as a protective fungicide. Formulation types SL (hydrochloride). Supplementary Entries – Extended prothoate 451 PRODUCTS: Discontinued products ‘Dynone’* (Schering); ‘Previcur’* (hydrochloride) (Schering). ANALYSIS: Product analysis by argentometric titration of the ethanethiol liberated by hydrolysis. Residues determined by the fuorimetric measurement of the N,N-dimethylpropane-1,3- diamine liberated by alkaline hydrolysis. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 76 (1988) is a general review of thiocarbamates. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Hydrochloride: Acute oral LD 50 for rats 1300, mice 660–1200 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1470, rabbits >980 (both as mg a.i. as formulation/kg). NOEL (90 d) for rats 0.5 mg/kg diet, for dogs 1.8 mg/kg diet. Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22| N; R51, R53 (hydrochloride) prothoate Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name prothoate (BSI, E-ISO, (m) F-ISO) IUPAC name O,O-diethyl S-isopropylcarbamoylmethyl phosphorodithioate; 2-diethoxyphosphinothioylthio-N-isopropylacetamide Chemical Abstracts name O,O-diethyl S-[2-[(1-methylethyl)amino]-2-oxoethyl] phosphorodithioate Other names trimethoate CAS RN [2275–18–5] EC no 218–893–2 Development codes E.I. 18 682 (Cyanamid); L 343 (Montedison) Smiles code CCOP(=S)(OCC)SCC(=O)NC(C)C PHYSICAL CHEMISTRY: Mol. wt. 285.4 M.f. C 9 H 20 NO 3 PS 2 Form Colourless crystals with a camphor-like odour; (tech. is an amber to yellow semi-solid). M.p. 28.5 °C; (tech.: 21–24 °C) V.p. 13 mPa (40 °C) S.g./density 1.151 (32 °C) Solubility In water 2.5 g/l (20 °C, tech.). Miscible with most organic solvents e.g. hexane, cyclohexane, higher petroleum FRACtions <30, light petroleum <20, glycerol <10 (all in g/kg, 20 °C). Stability Stable at 4.0<pH<8.2, but decomposed at 50 °C inc. 48 h at pH 9.2. Tech. is stable to light and at ≤60 °C. F.p. 160 °C S P(OCH 2 CH 3 ) 2 S CH 2 C (CH 3 ) 2 CHNH O 452 The Pesticide Manual Sixteenth Edition © BCPC 2012 proxan; proxan-sodium COMMERCIALISATION: History Insecticide reported (Ital. Agric., 1955, 99, 747). Discovered by American Cyanamid Co. and later introduced by Montecatini S.p.A. (later Agrimont S.p.A.). Patents US 2494283 (to Cyanamid); GB 791824 (to Montedison) APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic acaricide and insecticide with contact and stomach action. Uses Control of mites, aphids, thrips, Lace bugs, and other sucking insect pests on a range of crops, including fruit trees, citrus, vegetables, cotton, ornamentals, sugar beet, sugar cane, tobacco, and vines. Formulation types EC; WP; SL; DP; GR . Compatibility Not compatible with highly alkaline materials. PRODUCTS: Discontinued products ‘Fac’* (Agrimont); Discontinued mixtures ‘Erysit Super’* (+ chlorfenson) (Schering); ‘Fac Super’* (+ chlorfenson) (Sopra). ANALYSIS: Product analysis by glc (B. Bazzi, Anal. Methods Pestic. Plant Growth Regul., 1976, 8, 213). Residues on crops are determined by glc (B. Bazzi, loc. cit.; B. Bazzi et al., Pestic. Sci., 1974, 5, 511). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 8.0, female rats 8.9, mice 19.8–20.3 mg/kg. Skin and eye Acute percutaneous LD 50 for rats 655, rabbits 100–200 mg/kg. Inhalation LC 50 (4 h) for rats 0.0029 mg/l air. NOEL (90 d) for rats 0.5 mg/kg daily, for mice 1 mg/kg daily. Toxicity Class WHO (a.i.) Ia EPA (formulation) I EC Classifcation T+; R27/28| R52, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 22.5 mg/kg, pheasants 18.8 mg/kg, wild ducks 11.9 mg/kg. Fish LC 50 (96 h) for goldfsh 33, trout 20, guppies 14 mg/l. Bees Dangerous to bees. proxan; proxan-sodium Herbicide NOMENCLATURE: Common name proxan (E-ISO from 1990, BSI, Canada, New Zealand); proxane ((m) F-ISO from 1990); IPX (WSSA) IUPAC name O-isopropyl hydrogen dithiocarbonate Supplementary Entries – Extended proximpham 453 Chemical Abstracts name O-(1-methylethyl) hydrogen carbonodithioate CAS RN [108–25–8] proxan; [140–93–2] proxan-sodium EC no 205–443–5 sodium salt PHYSICAL CHEMISTRY: Mol. wt. 136.2; (sodium salt 158.2) M.f. C 4 H 8 OS 2 ; (sodium salt C 4 H 7 NaOS 2 ) COMMERCIALISATION: History Herbicide reported by L. L. Baumgartner & B. Wolf (Contrib. Boyce Thompson Inst., 1949, 15, 403). Introduced by Goodrich Chemical Co. PRODUCTS: Discontinued products ‘Goodriten.i.x.’* (Goodrich). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22| Xi; R38| N; R51, R53 (sodium salt) proximpham Herbicide NOMENCLATURE: Chemical Abstracts name 2-propanone O-[(phenylamino)carbonyl]oxime CAS RN [2828–42–4] Smiles code CC(=NOC(=O)Nc1ccccc1)C PHYSICAL CHEMISTRY: Mol. wt. 192.2 M.f. C 10 H 12 N 2 O 2 Form Colourless crystals. M.p. 109.5 °C V.p. 6.7 × 10 –1 mPa (20 °C) Henry 2.58 × 10 –4 Pa m 3 mol –1 (20 °C, calc.) S.g./density 1.02 Solubility In water 500 mg/l (20 °C). Readily soluble in common organic solvents, e.g. in methanol 43, DMF 41, ethanol 36, acetone 35, benzene 34, toluene 9, diethyl ether 5 (g/100g). Practically insoluble in hexane. Stability Stable up toc. 90 °C. In acidic media, hydrolysed to aniline and diphenylurea; in alkaline media, hydrolysed to diphenyl urea and acetone oxime; in neutral aqueous solution, DT 50 13 d. COMMERCIALISATION: Manufacturers Fahlberg-List APPLICATIONS: Uses Selective pre-emergence or pre-planting control of annual weeds in beet crops,corn salad, lettuce and spinach as well as in the seeding of Scots pine and spruce. Only used in mixed formulations. ANALYSIS: PRODUCTS: determined by gc with FID (D. Spengler & A. Jumar, Arch. Pfanzenschutz 1969, 5, 445) or titration of the iodine liberated by acid hydrolysis in the presence of N O O N H 454 The Pesticide Manual Sixteenth Edition © BCPC 2012 PT807 iodide. Residues in soil by extraction with acetone, isolation and separation from other herbicides by tlc, saponifcation with semi-concentrated sulfuric acid, diazotisation, coupling with N-(1-naphthyl)ethylenediamine dihydrochloride, and spectrophotometric measurement of the extinction at 550 nm (D. Spengler & A. Jumar, J. Chromatogr. 1970, 49, 329). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1540, mice 1300 mg/kg. NOEL (90 d) for rats 100 mg/kg. ECOTOXICOLOGY: Fish LC 50 (48 h) for guppies 93 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Soil/Environment In soil, there is partly microbial, partly hydrolytic degradation; DT 50 7–10 d. Aniline is not found. prynachlor Herbicide NOMENCLATURE: Common name prynachlore ((m) F-ISO); prynachlor (BSI, E-ISO, ANSI, WSSA) IUPAC name 2-chloro-N-(1-methylprop-2-ynyl)acetanilide Chemical Abstracts name 2-chloro-N-(1-methyl-2-propynyl)-N- phenylacetamide CAS RN [21267–72–1] Development codes BAS 290H (BASF) Smiles code CC(C#C)N(C(=O)CCl)c1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 221.7 M.f. C 12 H 12 ClNO COMMERCIALISATION: History Herbicide developed by BASF AG. PRODUCTS: Discontinued products ‘Basamaize’* (BASF). PT807 Plant growth regulator Most data here are taken from the EPA Fact Sheet. NOMENCLATURE: Chemical Abstracts name N,N-diethyl-2-(4-methylbenzyloxy)ethylamine hydrochloride Other names MBTA CAS RN [274671–61–3] Development codes PT807 PHYSICAL CHEMISTRY: Composition Except where stated otherwise, data are for the hydrochloride salt. Supplementary Entries – Extended PT807 455 Mol. wt. 221.3 M.f. C 14 H 23 NO (free base) Form Colourless slightly viscous liquid. B.p. 105.9±1.5 °C V.p. 1.19 × 10-2 mPa (EPA Fact Sheet) K ow logP <0 (pH 5 and 7), 2.0–2.4 (pH 9) (EPA Fact Sheet) S.g./density 1.0596 Solubility Miscible with water (pH 5–9). Miscible with acetonitrile, methanol, dichloromethane and octanol (25 °C). Stability Stable to hydrolysis. pKa 9.55 COMMERCIALISATION: History Plant growth regulator. First registered in USA in 1999; registration cancelled in 2004. Manufacturers GMJA APPLICATIONS: Mode of action Systemic. Uses Promotes sugar accumulation in processing oranges and shortens the time to maturation; applied at 0.013 lb/a. Formulation types SC. PRODUCTS: Discontinued products ‘Ecolyst’* (GMJA). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EPA Fact Sheet, Jan. 2000. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 531 mg/kg. Skin and eye Slight to moderate eye irritant; not a skin irritant. Not a skin sensitiser. NOEL Acute neurotoxicity NOAEL for rats 50 mg/kg daily. Reproductive NOAEL for rats 14 mg/kg daily. (EPA Fact Sheet). ADI/RfD (EPA) aRfD 0.5, cRfD 0.14 mg/kg b.w. [2000]. ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 765 mg/kg. Dietary LC 50 (8 d) for bobwhite quail and mallard ducks >5600 ppm. Fish LC 50 (96 h) for rainbow trout 6.7, bluegill sunfsh >12.6, sheepshead minnows 16 mg/l. Daphnia LC 50 (24 h) 24 mg/l. Algae IC50 (96 h) for Pseudokirchneriella subcapitata 0.40, Skeletonema costatum 0.119, Navicula pelliculosa 0.88 mg/l. Other aquatic spp. EC 50 (96 h) for eastern oysters 7.0, mysid shrimps 20 mg/l. IC50 (96 h) for Lemma gibba >116 mg/l. Bees LD 50 for honeybees >25 μg/bee. ENVIRONMENTAL FATE: Animals After administration to rats, rapidly metabolised and excreted, primarily in the urine; only minor amounts of parent were identifed in urine and faeces. The primary metabolite was a carboxylic acid metabolite, which then undergoes conjugation to glucuronic acid, or hydroxylation on the alkyl portion of the molecule. Soil/Environment Stable to photolysis. Soil DT 50 (aerobic metabolism) 335 d; the primary degradation pathway is aerobic degradation to CO 2 . Persistent, moderately mobile to immobile; K oc 285–11 000. 456 The Pesticide Manual Sixteenth Edition © BCPC 2012 pyfubmide pydanon Plant growth regulator NOMENCLATURE: Common name pydanon (BSI, E-ISO, (m) F-ISO) IUPAC name (±)-hexahydro-4-hydroxy-3,6-dioxopyridazin-4-ylacetic acid Chemical Abstracts name hexahydro-4-hydroxy-3,6-dioxo-4-pyridazineacetic acid CAS RN [22571–07–9] unstated stereochemistry Development codes H 1244 Smiles code OC(=O)CC1(O)CC(=O)NNC1=O PHYSICAL CHEMISTRY: Mol. wt. 188.1 M.f. C 6 H 8 N 2 O 5 M.p. 98 °C V.p. Negligible (room temperature) Solubility Readily soluble in water. COMMERCIALISATION: History Plant growth regulator developed by C. F. Spiess & Sohn. APPLICATIONS: Mode of action Plant growth regulator. rapidly absorbed by leaves and roots and translocated acropetally and basipetally. Uses Applied to young plants to delay general development for 1–3 w. Applied before bud break, causing retardation of blossom for 1–2 w. Also prevents chlorosis of seedlings inside containers. MAMMALIAN TOXICOLOGY: Oral Oral LD 50 for mice 1000 mg/kg. Toxicity Class WHO (a.i.) O pyfubmide NOMENCLATURE: Common name pyfubumide (pa ISO) IUPAC name 3′-isobutyl-N-isobutyryl-1,3,5-trimethyl-4′-[2,2,2-trifuoro-1-methoxy-1- (trifuoromethyl)ethyl]pyrazole-4-carboxanilide O OH HN H N O O OH CF 3 F 3 C O N O N N CH 3 C H 3 CH 3 O CH 3 C H 3 C H 3 CH 3 CH 3 Supplementary Entries – Extended pyracarbolid 457 Chemical Abstracts name 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2- methylpropyl)-4-[2,2,2-trifuoro-1-methoxy-1-(trifuoromethyl)ethyl]phenyl]-1H- pyrazole-4-carboxamide CAS RN [926914–55–8] Development codes NNI–0711 Smiles code Cc1c(c(n(n1)C)C)C(=O)N(c2ccc(c(c2)CC(C)C)C(C(F)(F)F)(C(F)(F)F)OC) C(=O)C(C)C PHYSICAL CHEMISTRY: Mol. wt. 535.52 M.f. C 25 H 31 F 6 N 3 O 3 pyracarbolid Fungicide NOMENCLATURE: Common name pyracarbolide ((m) F-ISO); pyracarbolid (BSI, E-ISO) IUPAC name 3,4-dihydro-6-methyl-2H-pyran-5-carboxanilide Chemical Abstracts name 3,4-dihydro-6-methyl-N-phenyl-2H-pyran-5-carboxamide CAS RN [24691–76–7] EC no 246–419–4 Development codes Hoe 13 764; Hoe 02 989 *; Hoe 6052 *; Hoe 6053 * Smiles code CC1=C(CCCO1)C(=O)Nc2ccccc2 PHYSICAL CHEMISTRY: Composition Tech. is ≥98%. Mol. wt. 217.3 M.f. C 13 H 15 NO 2 Form Colourless solid. M.p. 110–111 °C V.p. 0.016 mPa (25 °C) Solubility In water 0.6 g/l (40 °C). In chloroform 366, ethanol 89, ethyl acetate 86, hexane 0.1, xylene 13 (all in g/l, 25 °C). Stability Stable to light and heat and in alkaline media, but decomposed by acids. COMMERCIALISATION: History Fungicide reported by H. Stingle et al. (Int. Congr. Plant Prot., 7th, Paris, 1970, p. 205 (Abstr.)) and B. Jank & F. Grossman (Pestic. Sci., 1971, 2, 43). Introduced by Hoechst AG. Patents DE 1668899; GB 1194526 APPLICATIONS: Mode of action Systemic fungicide, absorbed by plants via roots and leaves. Uses Effective against Basidiomycetes. It controls Rusts (Uredinales), Smuts (Ustilaginales), and Damping-off disease caused by Thanatephorus cucumeris (Rhizoctonia solani). It is used in bean, cereal, coffee, and tea crops. Rates and concentrations vary considerably depending on disease/crop combination and formulation. Formulation types SC. WP; Seed treatment. PRODUCTS: Discontinued products ‘Sicarol’* (Hoechst). ANALYSIS: Product analysis is by titration. Residues may be determined by colorimetric methods. 458 The Pesticide Manual Sixteenth Edition © BCPC 2012 pyriclor MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for female rats >15 000 mg (in starch mucilage)/kg. Skin and eye Acute percutaneous LD 50 for female rats >1000 mg/kg. NOEL (2 y) for rats 400, dogs 1600 mg/kg diet. Other Acute i.p. LD 50 for female rats 1600 mg/kg. Toxicity Class WHO (a.i.) U EC Classifcation R52, R53 ECOTOXICOLOGY: Fish LC 50 (96 h) for carp 42.3, rainbow trout 45.5 mg/l. pyresmethrin Insecticide IRAC 3 NOMENCLATURE: Common name pyresmé(thrine) ((f) F-ISO); pyresmethrin (BSI, E-ISO) IUPAC name 5-benzyl-3-furylmethyl (E)-(1R)-trans-3-(2-methoxycarbonylprop-1- enyl)-2,2-dimethylcyclopropanecarboxylate; 5-benzyl-3-furylmethyl (E)-(1R,3R)-3-(2- methoxycarbonylprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate Chemical Abstracts name [1R-[1α,3β(E)]]-[5-(phenylmethyl)-3-furanyl]methyl 3-(3-methoxy-2-methyl-3-oxo-1-propenyl)-2,2-dimethylcyclopropanecarboxylate CAS RN [24624–58–6], formerly [56194–68–4] and [20425–39–2] Development codes NRDC 106; RU-12061 Smiles code COC(=O)C(=CC1C(C(=O)OCc2coc(Cc3ccccc3)c2)C1(C)C)C PHYSICAL CHEMISTRY: Mol. wt. 382.5 M.f. C 23 H 26 O 5 COMMERCIALISATION: History Insecticide discovered by M. Elliott et al. APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. pyriclor Herbicide NOMENCLATURE: Common name pyriclor (WSSA) IUPAC name 2,3,5-trichloropyridin-4-ol Chemical Abstracts name 2,3,5-trichloro-4-pyridinol CAS RN [1970–40–7] Smiles code Oc1c(Cl)cnc(Cl)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 198.4 M.f. C 5 H 2 Cl 3 NO Supplementary Entries – Extended pyridafol 459 COMMERCIALISATION: History Herbicide reported by M. J. Huraux & H. M. Lawson (Symp. New Herbic., 2nd, 1965, p. 269). Introduced by Dow Chemical Co. (later DowElanco). APPLICATIONS: Mode of action Translocated herbicide. PRODUCTS: Discontinued products ‘Daxtron’* (Dow). pyridafol Herbicide HRAC C3; phenylpyridazine NOMENCLATURE: Common name pyridafol (BSI, E-ISO, (m) F-ISO) IUPAC name 6-chloro-3-phenylpyridazin-4-ol Chemical Abstracts name 6-chloro-3-phenyl-4-pyridazinol CAS RN [40020–01–7] EC no 254–752–1 Development codes NOA 402 989; SAN 1367H PHYSICAL CHEMISTRY: Mol. wt. 206.6 M.f. C 10 H 7 ClN 2 O COMMERCIALISATION: History Herbicide evaluated by Novartis Crop Protection AG. APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, application withdrawn. ENVIRONMENTAL FATE: Soil/Environment In soil, formed as a degradate of pyridate, q.v. for details. N N Cl OH 460 The Pesticide Manual Sixteenth Edition © BCPC 2012 pyrifenox pyridinitril Fungicide NOMENCLATURE: Common name pyridinitril (BSI, E-ISO); DDPP (JMAF); pyridinitrile ((m) F-ISO) IUPAC name 2,6-dichloro-4-phenylpyridine-3,5-dicarbonitrile Chemical Abstracts name 2,6-dichloro-4-phenyl-3,5-pyridinedicarbonitrile CAS RN [1086–02–8] Development codes IT 3296 Smiles code Clc1nc(Cl)c(C#N)c(c1C#N)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 274.1 M.f. C 13 H 5 Cl 2 N 3 COMMERCIALISATION: History Fungicide reported by G. Mohr et al. (Meded. Rijksfac. Landbouwwet. Gent, 1968, 33, 1293). Introduced by E. Merck (later Shell Agrar GmbH). APPLICATIONS: Mode of action Protective fungicide. PRODUCTS: Discontinued mixtures ‘Ciluan’* (+ captan) (E. Merck). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O pyrifenox Fungicide FRAC 3, G1; SBI Class I, DMI: pyridine NOMENCLATURE: Common name pyrifé(nox) ((m) F-ISO); pyrifenox (BSI, ANSI, E-ISO) IUPAC name 2′,4′-dichloro-2-(3-pyridyl)acetophenone (E,Z)-O-methyloxime Chemical Abstracts name 1-(2,4-dichlorophenyl)-2-(3-pyridinyl)ethanone O-methyloxime CAS RN [88283–41–4] Development codes Ro 15–1297; ACR 3651 A (both Dr Maag); CGA 179945 (Ciba); NRK-297 (Nippon Kayaku) Smiles code CON=C(Cc1cccnc1)c2ccc(Cl)cc2Cl PHYSICAL CHEMISTRY: Composition A mixture of (E)- and (Z)- isomers. Mol. wt. 295.2 M.f. C 14 H 12 Cl 2 N 2 O N CH 2 C N CH 3 O Cl Cl Supplementary Entries – Extended pyrifenox 461 Form Pale yellow, viscous liquid, with a slightly sweet odour. B.p. 212.1 °C V.p. 1.7 mPa (25 °C) K ow logP = 3.4 (pH 5.0), 3.7 (pH 7.0), 3.7 (pH 9.0) (all 25 °C) S.g./density 1.28 (20 °C) Solubility In water 300 (pH 5.0), 150 (pH 6.7), 130 (pH 9.0) (all in mg/l, 25 °C). In n-hexane 210 g/l (25 °C). Completely miscible with ethanol, acetone, toluene and n-octanol. Stability Stable for >3 years in a closed container at room temperature. Stable to uv light and to hydrolysis in water (pH 3, 7, 9; 50 °C). pKa 4.61, weak base F.p. 106 °C (1013 mbar) COMMERCIALISATION: History Fungicide reported by P. Zobrist et al. (Proc. Br. Crop Prot. Conf. - Pests Dis., 1986, 1, 47). Introduced by Dr R Maag Ltd and frst marketed in 1986. Patents EP 49854 Manufacturers Syngenta APPLICATIONS: Biochemistry Ergosterol biosynthesis inhibitor. Mode of action Systemic fungicide with protective and curative action. Absorbed by the leaves and roots, and translocated acropetally. Uses Systemic Fungicide used, at 40–150 g/ha, for the control of powdery mildew, scab and other pathogenic Ascomycetes, Basidiomycetes and Deuteromycetes on grapes, cucurbits, pome fruit, stone fruit, peanuts, sugar beet, ornamentals and vegetables. Formulation types EC; WG; WP. PRODUCTS: Discontinued products ‘Corado’* (Ciba); ‘Corona’* (Syngenta); ‘Curado’* (Ciba); ‘Dorado’* (Syngenta); ‘Podigrol’* (Syngenta); Discontinued mixtures ‘Furado’* (+ mancozeb) (Ciba); ‘Rondo’* (+ captan) (Syngenta). ANALYSIS: Product analysis by tlc, glc, or hplc; glc with FID is recommended. Residues determined by lc, glc or hplc. See R. P. Hanni & A. J. Schuler, in Comp. Anal. Profles, Chapt. 3. Details also available from Syngenta. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: J. Pestic. Sci., 1991, 16, 355–359. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2912, mice >2000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Weak irritant to skin (humans); non-irritant to eyes (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 (4 h) for rats >2048 mg/m 3 air. NOEL (2 y) for rats 15 mg/kg b.w. daily; (1.5 y) for mice 45 mg/kg b.w. daily; (1 y) for dogs 10 mg/kg b.w.. daily. ADI/RfD (BfR) 0.09 mg/kg b.w. [1991]; (EPA) 0.01 mg/kg b.w. [1987]. Other Not mutagenic, not teratogenic, and not oncogenic. Toxicity Class WHO (a.i.) III ECOTOXICOLOGY: Birds Acute oral LD 50 (14 d) for mallard ducks and bobwhite quail >2000 mg/kg. Fish LC 50 (96 h) for rainbow trout 7.1, mirror carp 12.2, bluegill sunfsh 6.6 mg/l. Daphnia EC 50 (48 h) 3.6 mg/l. Algae EC 50 (96 h) for Scenedesmus subspicatus 0.095 mg/l. Bees LD 50 (48 h) (oral) 59 μg/bee; (contact) 70 μg/bee. Worms LC 50 (14 d) 462 The Pesticide Manual Sixteenth Edition © BCPC 2012 pyriminostrobin for earthworms 733 mg/kg. Other benefcial 200 g/l EC formulation harmless to Typhlodromus pyri and Orius insidiosus; slightly toxic to Coccinella septempunctata and Trichogramma cacoeciae (IOBC). ENVIRONMENTAL FATE: Animals In rats, following oral administration, pyrifenox is rapidly absorbed, metabolised and excreted in the urine and faeces. There are no indications of bioretention in tissue or organs. Plants Relatively rapid degradation in plants. DT 50 in peanut leaves 4 d, apple leaves 3 d, apple fruit 9 d. The main degradation pathway is by hydrolysis and elimination of the oxime group. Soil/Environment Moderate soil mobility, no tendency toward bioaccumulation, little potential for environmental persistence, and fairly rapid dissipation in plants, soil, water and animals. See R. P. Hanni & A. J. Schuler, in Comp. Anal. Profles, Chapt. 3. DT 50 in soil 50–120 d, K oc 980 ml/g soil. pyriminostrobin Acaricide NOMENCLATURE: Common name pyriminostrobin (pa ISO) IUPAC name methyl (E)-2-{α-[2-(2,4-dichloroanilino)-6-(trifuoromethyl)pyrimidin-4- yloxy]-o-tolyl}-3-methoxyacrylate Chemical Abstracts name methyl (αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6- (trifuoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate CAS RN [1257598–43–8] Development codes SYP–11277 Smiles code InChI=1S/C23H18Cl 2 F3N3O4/c1-33-12-16(21(32)34-2)15-6-4-3-5- 13(15)11-35-20-10 –1 9(23(26,27)28)30-22(31-20)29-18-8-7-14(24)9-17(18)25/h3- 10,12H,11H2,1-2H3,(H,29,30,31)/b16-12+ PHYSICAL CHEMISTRY: Mol. wt. 528.31 M.f. C 23 H 18 Cl 2 F 3 N 3 O 4 CF 3 H O C H 3 O CH 3 O O N NH N Cl Cl Supplementary Entries – Extended pyrinuron 463 pyrimitate Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name pyrimitate (BSI, E-ISO, (m) F-ISO, BAN (from 1985)); pyrimithate* (BAN before 1985) IUPAC name O-2-dimethylamino-6-methylpyrimidin-4-yl O,O-diethyl phosphorothioate Chemical Abstracts name O-[2-(dimethylamino)-6-methyl-4-pyrimidinyl] O,O- diethyl phosphorothioate CAS RN [5221–49–8] Development codes ICI 29 661 Smiles code CCOP(=S)(OCC)Oc1cc(C)nc(n1)N(C)C PHYSICAL CHEMISTRY: Mol. wt. 305.3 M.f. C 11 H 20 N 3 O 3 PS COMMERCIALISATION: History Veterinary insecticide and acaricide introduced by ICI Pharmaceuticals Division. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses For veterinary use. PRODUCTS: Discontinued products ‘Diothyl’* (ICI). pyrinuron Rodenticide NOMENCLATURE: Common name pyrinuron (BSI, E-ISO, (m) F-ISO, ANSI); piriminil (JMAF) IUPAC name 1-(4-nitrophenyl)-3-(3-pyridylmethyl)urea Chemical Abstracts name N-(4-nitrophenyl)-N′-(3-pyridinylmethyl)urea CAS RN [53558–25–1] Development codes RH-787 Smiles code [O-][N+](=O)c1ccc(NC(=O)NCc2cccnc2)cc1 PHYSICAL CHEMISTRY: Mol. wt. 272.3 M.f. C 13 H 12 N 4 O 3 COMMERCIALISATION: History Rodenticide evaluated by Rohm & Haas Co. PRODUCTS: Discontinued products ‘Vacor’* (Rohm & Haas). 464 The Pesticide Manual Sixteenth Edition © BCPC 2012 pyrisoxazole pyriprole Insecticide NOMENCLATURE: Common name pyriprole (BSI, E-ISO, (m) F-ISO) IUPAC name 1-(2,6-dichloro-α,α,α-trifuoro-p-tolyl)-4-(difuoromethylthio)-5-[(2- pyridylmethyl)amino]pyrazole-3-carbonitrile Chemical Abstracts name 1-[2,6-dichloro-4-(trifuoromethyl)phenyl]- 4-[(difuoromethyl)thio]-5-[(2-pyridinylmethyl)amino]-1H-pyrazole-3- carbonitrile CAS RN [394730–71–3] Development codes V3086 Smiles code N#CC1=NN(C2=C(Cl)C=C(C(F)(F)F)C=C2Cl) C(NCC3=NC=CC=C3)=C1SC(F)F PHYSICAL CHEMISTRY: Mol. wt. 494.3 M.f. C 18 H 10 Cl 2 F 5 N 5 S COMMERCIALISATION: History Under development as an insecticide. Patents EP 1310497; US 7371768. APPLICATIONS: Uses Control of Lepidoptera and Coleoptera. pyrisoxazole Fungicide FRAC 3, G1; SBI Class I, DMI: pyridine NOMENCLATURE: Common name pyrisoxazole (pa ISO) N N N N H N S F F F F F Cl Cl C H 3 C H 3 Cl N N O Supplementary Entries – Extended pyroxyfur 465 IUPAC name 3-[(3R,5RS)-5-(4-chlorophenyl)-2,3-dimethyl-1,2-oxazolidin-3-yl]pyridine Chemical Abstracts name 3-[(3R)-5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl] pyridine CAS RN [291771–99–8] (3R,5R)- isomer; [291771–83–0] (3R,5S)- isomer Development codes SYP-48 Smiles code C[C@@]1(CC(ON1C)c2ccc(cc2)Cl)c3cccnc3 PHYSICAL CHEMISTRY: Mol. wt. 288.77 M.f. C 16 H 17 ClN 2 O pyroxychlor Fungicide NOMENCLATURE: Common name pyroxychlor (BSI, E-ISO, ANSI); pyroxychlore ((m) F-ISO) IUPAC name 2-chloro-6-methoxy-4-trichloromethylpyridine; 6-chloro-4-trichloromethyl- 2-pyridyl methyl ether Chemical Abstracts name 2-chloro-6-methoxy-4-(trichloromethyl)pyridine CAS RN [7159–34–4] Development codes Dowco 269 Smiles code COc1cc(cc(Cl)n1)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 260.9 M.f. C 7 H 5 Cl 4 NO COMMERCIALISATION: History Fungicide evaluated by Dow Chemical Co. (later DowElanco). PRODUCTS: Discontinued products ‘Lorvek’* (Dow); ‘Nurelle’* (Dow). pyroxyfur Fungicide NOMENCLATURE: Common name pyroxyfur (BSI, ANSI, E-ISO, (m) F-ISO) IUPAC name 6-chloro-4-trichloromethyl-2-pyridyl furfuryl ether Chemical Abstracts name 2-chloro-6-(2-furanylmethoxy)-4-(trichloromethyl) pyridine CAS RN [70166–48–2] Development codes Dowco 444 Smiles code Clc1cc(cc(OCc2ccco2)n1)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 327.0 M.f. C 11 H 7 Cl 4 NO 2 COMMERCIALISATION: History Fungicide evaluated by Dow Chemical Co. (later DowElanco). 466 The Pesticide Manual Sixteenth Edition © BCPC 2012 quinalphos-methyl PRODUCTS: Discontinued products ‘Grandstand’* (Dow). N-pyrrolidinosuccinamic acid Plant growth regulator NOMENCLATURE: IUPAC name N-pyrrolidinosuccinamic acid Chemical Abstracts name 4-oxo-4-(1-pyrrolidinylamino)butanoic acid CAS RN [23744–05–0] Development codes F 529 Smiles code OC(=O)CCC(=O)NN1CCCC1 PHYSICAL CHEMISTRY: Mol. wt. 186.2 M.f. C 8 H 14 N 2 O 3 COMMERCIALISATION: History Plant growth regulator evaluated by Uniroyal Chemical Co., Inc. APPLICATIONS: Mode of action Plant growth retardant. PRODUCTS: Discontinued products ‘FFive’* (Uniroyal). quinalphos-methyl Insecticide IRAC 1B NOMENCLATURE: Common name quinalphos-methyl (BSI, E-ISO, (m) F-ISO); chinalphos-mé(thyl) ((m) France) IUPAC name O,O-dimethyl O-quinoxalin-2-yl phosphorothioate Chemical Abstracts name O,O-dimethyl O-2-quinoxalinyl phosphorothioate CAS RN [13593–08–3] Development codes SAN 52 056I Smiles code COP(=S)(OC)Oc1cnc2ccccc2n1 PHYSICAL CHEMISTRY: Mol. wt. 270.2 M.f. C 10 H 11 N 2 O 3 PS COMMERCIALISATION: History Insecticide evaluated by Sandoz AG. For quinalphos, see Main entries. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Supplementary Entries – Extended quinonamid 467 quinazamid Fungicide NOMENCLATURE: Common name quinazamid (BSI, E-ISO); quinazamide ((m) F-ISO) IUPAC name p-benzoquinone monosemicarbazone Chemical Abstracts name 2-(4-oxo-2,5-cyclohexadien-1-ylidene)hydrazinecarboxamide CAS RN [61566–21–0] Development codes RD 8684; BTS 8684 Smiles code NC(=O)NN=C1C=CC(=O)C=C1 PHYSICAL CHEMISTRY: Mol. wt. 165.2 M.f. C 7 H 7 N 3 O 2 COMMERCIALISATION: History Fungicide evaluated by Boots Co., Ltd (later Schering Agrochemicals). quinconazole Fungicide NOMENCLATURE: Common name quinconazole (BSI, E-ISO, (m) F-ISO) IUPAC name 3-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)quinazolin-4(3H)-one Chemical Abstracts name 3-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)- 4(3H)-quinazolinone CAS RN [103970–75–8] Development codes SN 539 865 Smiles code Clc1ccc(c(Cl)c1)n2c(nc3ccccc3c2=O)n4cncn4 PHYSICAL CHEMISTRY: Mol. wt. 358.2 M.f. C 16 H 9 Cl 2 N 5 O COMMERCIALISATION: History Fungicide reported by C. R. Leake (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., 1, 343). Evaluated by Schering AG. APPLICATIONS: Biochemistry Sterol demethylation inhibitor. quinonamid Algicide NOMENCLATURE: Common name quinonamid (BSI, E-ISO); quinonamide ((m) F-ISO) IUPAC name 2,2-dichloro-N-(3-chloro-1,4-naphthoquinon-2-yl)acetamide Chemical Abstracts name 2,2-dichloro-N-(3-chloro-1,4-dihydro-1,4-dioxo-2- 468 The Pesticide Manual Sixteenth Edition © BCPC 2012 quinothion naphthalenyl)acetamide CAS RN [27541–88–4] Development codes Hoe 02 997 Smiles code ClC(Cl)C(=O)NC1=C(Cl)C(=O)c2ccccc2C1=O PHYSICAL CHEMISTRY: Composition Tech. is 97%. Mol. wt. 318.5 M.f. C 12 H 6 Cl 3 NO 3 Form Yellow needles. M.p. 214–216 °C V.p. 0.011 mPa (20 °C) Solubility In water 3.0 (pH 4.6), 60 (pH 7) (both mg/l, 23 °C). In acetonec. 7, ethanolc. 3, hexane 0.04, xylene 8 (all in g/l, 20 °C). Stability Decomposed by acid or alkali. COMMERCIALISATION: History Algicide reported by P. Hartz et al. (Meded. Fac. Landbouwwet. Rijksuniv. Gent, 1972, 37, 699). Introduced by Hoechst AG. Patents DE 1768447; GB 1263625 APPLICATIONS: Uses Effective against algae in the open as well as algae and mosses under glass. It could be used as a seed treatment or spray for control of algae in paddies, as a dip for clay pots, and for treating benches, etc., in greenhouses. Formulation types GR; WP. PRODUCTS: Discontinued products ‘Alginex’* (Hoechst); ‘Nosprasit’* (Hoechst). ANALYSIS: Product and residue analysis is by glc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 11 700–15 000 mg/kg. NOEL (90 d) for rats 2000 mg/kg diet. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Acute oral LD 50 for Japanese quail 11 136–15 542 mg/kg (depending on carrier and sex). Fish LC 50 (96 h) for rainbow trout 0.45 mg/l. quinothion Insecticide IRAC 1B NOMENCLATURE: Common name quinothion (BSI) IUPAC name O,O-diethyl O-2-methyl-4-quinolyl phosphorothioate Chemical Abstracts name O,O-diethyl O-(2-methyl-4-quinolinyl) phosphorothioate CAS RN [22439–40–3] Smiles code CCOP(=S)(OCC)Oc1cc(C)nc2ccccc12 PHYSICAL CHEMISTRY: Mol. wt. 311.3 M.f. C 14 H 18 NO 3 PS COMMERCIALISATION: History Insecticide introduced by Bayer AG. Supplementary Entries – Extended R-1492 469 APPLICATIONS: Biochemistry Cholinesterase inhibitor. quintiofos Insecticide IRAC 1B NOMENCLATURE: Common name quintiofos (BSI, E-ISO, (m) F-ISO, BAN) IUPAC name O-ethyl O-8-quinolyl phenylphosphonothioate Chemical Abstracts name O-ethyl O-8-quinolinyl phenylphosphonothioate CAS RN [1776–83–6] Development codes BAY 9037 Smiles code CCOP(=S)(Oc1cccc2cccnc12)c3ccccc3 PHYSICAL CHEMISTRY: Mol. wt. 329.4 M.f. C 17 H 16 NO 2 PS COMMERCIALISATION: History Insecticide introduced by Bayer AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Bacdip’* (Bayer). R-1492 Acaricide, insecticide IRAC 1B NOMENCLATURE: IUPAC name S-4-chlorophenylthiomethyl O,O-dimethyl phosphorodithioate Chemical Abstracts name S-[[(4-chlorophenyl)thio]methyl] O,O-dimethyl phosphorodithioate Other names methylcarbophenothione; methyl carbophenothion CAS RN [953–17–3] Development codes R-1492 (Stauffer); G-29288 (Geigy) Smiles code COP(=S)(OC)SCSc1ccc(Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 314.8 M.f. C 9 H 12 ClO 2 PS 3 Form Light yellow to amber liquid with a moderate mercaptan odour. M.p. c. –18 °C V.p. 400 mPa (25 °C) S.g./density 1.34–1.35 (20 °C) Solubility In water c. 1 mg/l (room temperature). Miscible with most organic solvents. Stability Moderately stable to heat and resistant to hydrolysis. 470 The Pesticide Manual Sixteenth Edition © BCPC 2012 RA-17 COMMERCIALISATION: History Insecticide and acaricide reported by J. A. Harding (J. Econ. Entomol., 1959, 52, 1219). Introduced by Stauffer Chemical Co. (later ICI Americas). Patents US 2793224. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic. Uses Acaricide similar in spectrum of activity to its analogue carbophenothion (q.v.), but more effective against cotton boll weevil; applied at 50–100 g/100 l. PRODUCTS: Discontinued products ‘Methyl Trithion’* (Stauffer); ‘TriMe’* (Stauffer). ANALYSIS: Product analysis by uv absorption methods, or by glc. For residues, see G. H. Batchelder et al., Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 2, 313; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 443. MAMMALIAN TOXICOLOGY: EC Classifcation T; R24/25| N; R50, R53| concn. dep. RA-17 Acaricide IRAC 1B NOMENCLATURE: IUPAC name N 2 -diethoxyphosphinothioyl-N 2 -ethyl-N1,N1-dipropylglycinamide Chemical Abstracts name O,O-diethyl [2-(dipropylamino)-2-oxoethyl] ethylphosphororamidothioate Other names phosglycin CAS RN [105084–66–0] Development codes RA-17 (ÉMV) Smiles code CCCN(CCC)C(=O)CN(CC)P(=S)(OCC)OCC PHYSICAL CHEMISTRY: Mol. wt. 338.4 M.f. C 14 H 31 N 2 O 3 PS Form Solid. M.p. 34 °C V.p. 1.8 mPa (25 °C) K ow logP = 3.9 Solubility In water 140 mg/l (20 °C). In acetone, benzene, chloroform, dichloromethane, ethanol, hexane >200 mg/l (20 °C). Stability Stable up to 180 °C. Degraded photochemically on silica gel plate (DT 50 18 h). COMMERCIALISATION: History Acaricide reported by K. Balogh & G. Tarpai (6th Int. Congr. Pestic. Chem., 1986). Introduced in Hungary (1987) by Északmagyarországi Vegyimüvek. Patents BE 903304; HU 2164940 N P(OCH 2 CH 3 ) 2 S CH 2 CON(CH 2 CH 2 CH 3 ) 2 CH 3 CH 2 Supplementary Entries – Extended rabenzazole 471 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses Effective against adults and larvae of phytophagous mites in apples (2.5 kg/ha), citrus (1–2 hg/ha) and grapes (2–3 kg/ha). Formulation types EC; WP. PRODUCTS: Discontinued products ‘Alkatox’* (Sagrochem). ANALYSIS: Product and residue analysis by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986) is a general review of organophosphorus insecticides. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2081, male mice 1800, female mice 1550 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Inhalation Non-toxic to rats at 0.59 mg/l air. ECOTOXICOLOGY: Fish LC 50 for carp 9.47, grass carp 12.5 mg/l, for sheat fsh 12 mg a.i. (as EC)/l. rabenzazole Fungicide NOMENCLATURE: Common name rabenzazole (BSI, E-ISO, (m) F-ISO) IUPAC name 2-(3,5-dimethylpyrazol-1-yl)benzimidazole Chemical Abstracts name 2-(3,5-dimethyl-1H-pyrazol-1-yl)-1H-benzimidazole CAS RN [40341–04–6] Smiles code Cc1cc(C)n(n1)c2nc3ccccc3[nH]2 PHYSICAL CHEMISTRY: Mol. wt. 212.3 M.f. C 12 H 12 N 4 COMMERCIALISATION: History Fungicide reported by W. Specht & M. Tillkes (Pfanz.-Nachr. Bayer (Engl. Ed.), 1980, 33, 61). Introduced by Bayer AG. PRODUCTS: Discontinued products ‘Ciriom’* (Bayer); Discontinued mixtures ‘Ciriom F’* (+ fuberidazole) (Bayer). 472 The Pesticide Manual Sixteenth Edition © BCPC 2012 RH 5849 rescalure Attractant NOMENCLATURE: Common name rescalure (pa ISO) IUPAC name (3RS,6RS;3RS,6SR)-6-isopropenyl-3-methyldec-9-en-1-yl acetate Chemical Abstracts name 3-methyl-6-(1-methylethenyl)-9-decen-1-yl acetate CAS RN [64309–03–1] Smiles code CC(CCC(CCC=C)C(=C)C)CCOC(=O)C PHYSICAL CHEMISTRY: Mol. wt. 252.39 M.f. C 16 H 28 O 2 RH 5849 Insecticide NOMENCLATURE: IUPAC name 2′-benzoyl-1′-tert-butylbenzohydrazide Chemical Abstracts name benzoic acid 2-benzoyl-1-(1,1-dimethylethyl)hydrazide CAS RN [112225–87–3] Development codes RH-5849 (Rohm & Haas) PHYSICAL CHEMISTRY: Mol. wt. 296.4 M.f. C 18 H 20 N 2 O 2 Form Colourless crystals. M.p. 174–176 °C V.p. 0.24 mPa (25 °C) K ow logP = 2.326 Solubility In water c. 50 mg/l. In cyclohexanonec. 50, mesityl oxidec. 150 g/l. Stability Stable under normal storage conditions. COMMERCIALISATION: History Insect growth regulator, of interest as the frst non-steroidal ecdysone agonist, reported by K. D. Wing (Science, 1988, 241, 467), K. D. Wing et al. (ibid., p. 470). Introduced by Rohm & Haas Co. Patents EP 236618 Manufacturers Rohm & Haas; Zhejiang Heyi O O CH 3 C H 3 CH 2 CH 2 CH 3 HN N O O C(CH 3 ) 3 Supplementary Entries – Extended RU 25475 473 APPLICATIONS: Biochemistry Non-steroidal ecdysone agonist. Mode of action Induces premature moulting at any point in larval development. Inhibits feeding and oviposition. Uses Control of colorado beetles on potatoes, pear leaf blister moths, leaf miners on apples and other crops, gypsy moths, codling moths, Mexican bean beetles, cutWorms, rice stem borers, ArmyWorms, boll weevils and housefies. Formulation types SC. GR . MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 435 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. Not irritant to skin or eyes of rabbits. Other Not mutagenic in Ames assay. ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks and quail >5000 mg/kg diet. Fish LC 50 (96 h) for bluegill sunfsh and trout >100 mg/l. Daphnia LC 50 (48 h) 7 mg/l; for life cycle 0.5–0.7 mg/l. Bees LD 50 (contact) >0.1 μg/bee. ENVIRONMENTAL FATE: Soil/Environment In silt loam DT 50 27 d (23 °C). rhodethanil Herbicide NOMENCLATURE: Common name rhodethanil (BSI, E-ISO); rodé(thanil) ((m) F-ISO) IUPAC name 3-chloro-4-ethylaminophenyl thiocyanate Chemical Abstracts name 3-chloro-4-(ethylamino)phenyl thiocyanate CAS RN [3703–46–6] Development codes BAY 5396 b H; BAY 53 427 Smiles code CCNc1ccc(SC#N)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 212.7 M.f. C 9 H 9 ClN 2 S COMMERCIALISATION: History Herbicide evaluated by Bayer AG. RU 25475 Insecticide IRAC 3 NOMENCLATURE: IUPAC name (S)-α-cyano-3-phenoxybenzyl (1R,3S)-[(RS)-1,2-dibromo-2,2- dichloroethyl]-2,2-dimethylcyclopropanecarboxylate; Roth: (S)-α-cyano-3-phenoxybenzyl (1R)-trans-3-((RS)-1,2-dibromo-2,2-dichloroethyl)-2,2-dimethylcyclopropanecarboxylate 474 The Pesticide Manual Sixteenth Edition © BCPC 2012 ryanodine Chemical Abstracts name cyano(3-phenoxyphenyl)methyl 3-(1,2-dibromo-2,2- dichloroethyl)-2,2-dimethylcyclopropanecarboxylate Other names tralocythrin* (unaccepted common name) CAS RN [66841–26–7] unstated stereochemistry Development codes RU 25475; HAG 106 Smiles code CC1(C)C(C(Br)C(Cl)(Cl)Br)C1C(=O)OC(C#N)c2cccc(Oc3ccccc3)c2 PHYSICAL CHEMISTRY: Mol. wt. 576.1 M.f. C 22 H 19 Br 2 Cl 2 NO 3 COMMERCIALISATION: History Insecticide evaluated by Roussel Uclaf for use in cotton. APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. ryanodine Insecticide See also The Manual of Biocontrol Agents entry: 2:220 NOMENCLATURE: Chemical Abstracts name (3S,4R,4aR,6S,6aS,7S,8R,8aS,8bR,9S,9aS)-dodecahydro- 4,6,7,8a,8b,9a-hexahydroxy-3,6a,9-trimethyl-7-(1-methylethyl)-6,9-methanobenzo[1,2] pentaleno[1,6-bc]furan-8-yl 1H-pyrrole-2-carboxylate Other names ryania extract CAS RN [15662–33–6] ryanodine, formerly [1361–01–9], [1580–06–9], [25800–57–1] and [15800–60–9]; [94513–55–0] 9,21-dehydroryanodine; [8047–13–0] formerly ryania, now a deleted number for ryanodine EC no 239–732–2 Smiles code CC(C)C1(O)C(OC(=O)c2ccc[nH]2)C3(O)C4(O)C1(C)C5(O)CC3(C) C6(O)CCC(C)C(O)C46O5 PHYSICAL CHEMISTRY: Composition The main toxicant of ryania, the ground stemwood of the shrub Ryania speciosa; 9,21-dehydroryanodine and other ryanoids are also present in the crude plant extract. Mol. wt. 493.6 M.f. C 25 H 35 NO 9 M.p. 219–220 °C (decomp.) Solubility Soluble in water, ethanol, acetone, diethyl ether, chloroform; almost insoluble in benzene, light O CH 3 CH 3 OH OH CH 3 HO OH OH HO CH 3 CH 3 O H O NH Supplementary Entries – Extended salicylanilide 475 petroleum. Stability Relatively stable on exposure to light and air. Specifc rotation [α]D25 +26° COMMERCIALISATION: Production Extracted from the powdered stem of the tropical shrub Ryania speciosa. History Insecticidal activity of ryania reported by B. E. Pepper & L. A. Carruth (J. Econ. Entomol., 1945, 38, 59). Introduced by S. B. Penick & Co. Patents US 2400295 Manufacturers Dunhill APPLICATIONS: Biochemistry Thought to cause a release of calcium from the sarcoplasmic reticulum in skeletal muscles fbers which in turn leads to sustained muscle contraction and paralysis. Mode of action Active by ingestion and by contact. Uses Ryania was used for control of codling moth, European corn borer and citrus thrips in fruit and maize. Applied at 10–72 kg ryania/ha (20–145 g alkaloid/ha). Formulation types WP. PRODUCTS: Discontinued products ‘Natur-Gro R-50’* (AgriSystems International); ‘Natur-Gro Triple Plus’* (AgriSystems International); ‘Ryan 50’* (Dunhill); ‘Ryania’* (Penick); ‘Rynotox’* (Penick). ANALYSIS: Product analysis by uv spectroscopy after extraction by liquid-liquid partition. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 of ryania for rats 1200, mice 650 mg/kg. Lethal dose of ryanodine in dogs 0.4 mg/kg. NOEL In 150 d feeding trials, guinea-pigs and chickens receiving 10 g/kg diet suffered no toxic symptom. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R21/22| N; R50, R53 ECOTOXICOLOGY: Fish Toxic to fsh. salicylanilide Fungicide NOMENCLATURE: Common name salicylanilide (BSI, E-ISO, F-ISO, JMAF, accepted in lieu of a common name.) IUPAC name salicylanilide Chemical Abstracts name 2-hydroxy-N-phenylbenzamide CAS RN [87–17–2] Smiles code Oc1ccccc1C(=O)Nc2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 213.2 M.f. C 13 H 11 NO 2 476 The Pesticide Manual Sixteenth Edition © BCPC 2012 schradan COMMERCIALISATION: History Fungicide reported by R. G. Fargher et al. (Mem. Shirley Inst., 1930, 9, 37). Introduced by ICI Limited. APPLICATIONS: Mode of action Protective fungicide. PRODUCTS: Discontinued products ‘Shirlan’* (ICI). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O schradan Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name schradan (BSI, E-ISO, ESA, JMAF); schradane ((m) F-ISO) IUPAC name octamethylpyrophosphoric tetra-amide Chemical Abstracts name octamethyldiphosphoramide Other names OMPA CAS RN [152–16–9] EC no 205–801–0 Smiles code CN(C)P(=O)(OP(=O)(N(C)C)N(C)C)N(C)C PHYSICAL CHEMISTRY: Composition Tech. contains decamethyltriphosphoric triamide, ((CH3)2N)2PO.OPO. (N(CH3)2)OPO(N(CH3)2)2, (25–50%), which is also insecticidal, and other amides of higher phosphoric acids. Mol. wt. 286.3 M.f. C 8 H 24 N 4 O 3 P 2 Form Colourless, viscous liquid. M.p. 14–20 °C B.p. 118–122 °C /0.3 mmHg V.p.c. 100 mPa (25 °C) S.g./density 1.1343 (25 °C) Solubility Miscible with water and most organic solvents; slightly soluble in petroleum oils. Stability Stable to water and alkali, but hydrolysed under acid conditions to dimethylamine and orthophosphoric acid. COMMERCIALISATION: History Systemic insecticide discovered by G. Schrader & H. Küenthal (cited by G. Schrader, Phosphorsäure-Ester, p. 88). Introduced by Pest Control Ltd (later Schering Agriculture). Patents GB 631549, GB 652981. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide. Relatively inert as a contact insecticide. Uses Effective against sap-feeding insects and mites. Used as a soil drench for transplanted trees. PRODUCTS: Discontinued products ‘Pestox3’* (FBC); ‘PestoxIII’* (FBC); Discontinued mixtures ‘Sytam’* (+ dimefox) (with tris(dimethylamino)phosphine oxide) Supplementary Entries – Extended scilliroside 477 (Murphy, Wacker); ‘Terra Sytam’* (+ dimefox) (with tris(dimethylamino)phosphine oxide) (Murphy, Wacker). ANALYSIS: Product analysis CIPAC Handbook, 1983, 1B, 1795; mixture with dimefox, 1980, 1A, 334. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 9.1, female rats 42 mg/kg. Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R27/28 scilliroside Rodenticide NOMENCLATURE: Common name scilliroside (JMAF) IUPAC name 3β-(β-D-glucopyranosyloxy)-17β-(2-oxo-2H-pyran-5-yl)-14β-androst-4- ene-6β,8,14-triol 6-acetate Chemical Abstracts name (3β,6β)-6-acetyloxy-3-(β-D-glucopyranosyloxy)-8,14- dihydroxybufa-4,20,22-trienolide Other names red squill CAS RN [507–60–8] EC no 208–077–4 Smiles code CC(=O)OC1CC2(O)C(CCC3(C)C(CCC32O) c4ccc(=O)oc4)C5(C)CC(CC=C15)OC6OC(CO)C(O)C(O)C6O PHYSICAL CHEMISTRY: Composition The name scilliroside applies to a glycoside contained in the extract of the powdered bulbs of the red squill, Urginea (Scilla) maritima. Mol. wt. 620.7 M.f. C 32 H 44 O 12 Form Hydrated prisms (from aqueous methanol) which losec. 8% m/m in vacuo, giving a hemihydrate. M.p. 168–170 °C (hemihydrate) V.p. Very low Solubility Slightly soluble in water. Readily soluble in alcohols, ethylene glycol, dioxane and glacial acetic acid. Slightly soluble in ethyl acetate, acetone and chloroform. Practically insoluble in diethyl ether and petroleum ether. Stability Decomposes at 200 °C; bulbs should be dried at temperatures below 80 °C. Dried red squill powder loses its scilliroside O OH OH CH 2 OH O CH 3 OCOCH 3 OH CH 3 OH O O OH H H 478 The Pesticide Manual Sixteenth Edition © BCPC 2012 sebuthylazine content on storage and when exposed to the atmosphere. Specifc rotation [α]D20 –59° to –60° (methanol) COMMERCIALISATION: History Rodenticide. Red squill has been used since the 13th century. Scilliroside, the toxic principle, was isolated and identifed by A. Stoll & J. Renz (Helv. Chim. Acta, 1942, 25, 377; 1943, 26, 648). Chemistry and toxicology of cardiac glycosides reviewed by A. Stoll (Experientia, 1954, 10, 282). The two varieties of U. maritima, red squill and white squill, contain glycosides, but only the former was used against rats. APPLICATIONS: Biochemistry Activity may be due to metabolism to the aglycone, scillirosidin. Causes emesis, and affects the cardiovascular and central nervous systems. Its specifc toxicity to rats may be due to the inability of the rodent to vomit, a reaction squill induces in other animals. Mode of action Selective rodenticide with stomach action. Uses Control of most species of rodents, e.g. brown rats (Rattus norvegicus), black rats (Rattus rattus), house mice (Mus musculus), long-tailed feld mice (Apodemus sylvaticus), and Field voles (Microtus agrestis). Formulation types RB; GB. ANALYSIS: Product analysis by tlc, or by chromatographic separation on paper and, after elution, photometric assay (M. Wichtl & L. Fuchs, Arch. Pharm., 1962, 295, 361). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, 2004/129/EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 0.7, female rats 0.43 mg/kg (A. Stoll & J. Renz Helv. Chim. Acta, 1942, 25, 377; 1943, 26, 648). Dogs, cats, and pigs survived 16 mg/kg (S. A. Barnett et al., J. Hyg. 1949, 47, 431). In most mammals, with the exception of rodents, scilliroside is an emetic. Toxicity Class WHO (a.i.) Ia EPA (formulation) I EC Classifcation T+; R28 ECOTOXICOLOGY: Birds Fowls survived 400 mg/kg. sebuthylazine Herbicide NOMENCLATURE: Common name sebuthylazine (BSI, E-ISO, (f) F-ISO) N N N NH Cl NH 2-sec-butylamino-4-chloro-6-ethylamino-1,3,5-triazine Supplementary Entries – Extended secbumeton 479 IUPAC name N 2 -sec-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine; 2-sec- butylamino-4-chloro-6-ethylamino-1,3,5-triazine Chemical Abstracts name 6-chloro-N-ethyl-N′-(1-methylpropyl)-1,3,5- triazine-2,4-diamine CAS RN [7286–69–3] Development codes GS 13 528 Smiles code CCCCNc1nc(Cl)nc(NCC)n1 PHYSICAL CHEMISTRY: Mol. wt. 229.7 M.f. C 9 H 16 ClN 5 Form Colourless powder. M.p. 159–161 °C Solubility Sparingly soluble in water. Soluble in acetone, benzene, dioxane; very soluble in chloroform; slightly soluble in diethyl ether, ethanol. COMMERCIALISATION: History Herbicide introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). PRODUCTS: Discontinued mixtures ‘Vorox(i)Granulat 371’* (+ amitrole + atrazine) (Spiess). secbumeton Herbicide NOMENCLATURE: Common name secbumeton (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name N 2 -sec-butyl-N4-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine Chemical Abstracts name N-ethyl-6-methoxy-N′-(1-methylpropyl)-1,3,5-triazine-2,4- diamine CAS RN [26259–45–0] EC no 247–554–1 Development codes GS 14 254 (Geigy) Smiles code CCNc1nc(NC(C)CC)nc(OC)n1 PHYSICAL CHEMISTRY: Mol. wt. 225.3 M.f. C 10 H 19 N 5 O Form Colourless crystals. M.p. 86–88 °C V.p. 0.97 mPa (20 °C) Henry 3.64 × 10 –4 Pa m 3 mol –1 (calc.) S.g./density 1.105 (20 °C) Solubility In water 600 mg/l (20 °C). In acetone 400, dichloromethane 600, hexane 22, methanol 500, n-octanol 200, toluene 350 (all in g/l, 20 °C). Stability DT 50 (calc.) 30 d (pH 1), 175 d (pH 13) (20 °C). pKa 4.4 COMMERCIALISATION: History Herbicide reported by A. Gast & E. Fankhauser (Proc. Br. Weed Control Conf., 8th, 1966, p. 485). Introduced by J. R. Geigy S.A. (later Ciba-Geigy AG). Patents CH 337019; GB 814948 APPLICATIONS: Mode of action Total and selective herbicide, taken up by leaves and roots. Uses Controls mono- and di-cotyledonous weeds both annual and perennial. It was used in established lucerne either at 1–3 kg/ha or in combination with simazine. In combination with terbuthylazine it was suitable for non-cropped land. Formulation types WP. 480 The Pesticide Manual Sixteenth Edition © BCPC 2012 sesamex PRODUCTS: Discontinued products ‘Etazine’* (Ciba-Geigy); ‘Etazine 3585’* (Ciba-Geigy); ‘Sumitol’* (Ciba-Geigy); Discontinued mixtures ‘Etazine 3947’* (+ simazine) (Ciba-Geigy); ‘Primatol 3588’* (+ terbuthylazine) (Ciba-Geigy). ANALYSIS: Product analysis by glc or by acidimetric titration. Residues determined by glc with MCD or FPD (K. Ramsteiner et al., J. Assoc. Off. Anal. Chem., 1974, 57, 192; E. Knüsli, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1964, 4, 13). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2680 mg tech./kg. NOEL (90 d) for rats 640 mg/kg diet (c 43 mg/kg daily), for dogs 1600 mg/kg diet (40 mg/kg daily). Toxicity Class WHO (a.i.) U EC Classifcation Xn; R22| Xi; R36| N; R50, R53 sesamex Insecticide synergist NOMENCLATURE: Common name sesamex (ESA) IUPAC name 5-[1-[2-(2-ethoxyethoxy)ethoxy]ethoxy]-1,3-benzodioxole (I); 2-(1,3-benzodioxol-5-yloxy)-3,6,9-trioxaundecane Chemical Abstracts name (I) CAS RN [51–14–9] Smiles code CCOCCOCCOC(C)Oc1ccc2OCOc2c1 PHYSICAL CHEMISTRY: Mol. wt. 298.3 M.f. C 15 H 22 O 6 Form Straw-coloured liquid with a faint odour. B.p. 137–141 °C /0.08 mmHg Solubility Readily soluble in kerosine and dichlorodifuoromethane. Stability Unstable in sunlight and on powdered carriers. COMMERCIALISATION: History Synergist for pyrethroid insecticides reported by M. Beroza (J. Agric. Food Chem., 1956, 4, 49). Introduced by Shulton Inc. PRODUCTS: Discontinued products ‘Sesoxane’* (Shulton). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2000–2270 mg/kg. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22 Supplementary Entries – Extended simeton 481 sesasmolin Insecticide synergist NOMENCLATURE: Common name sesasmolin (ESA) IUPAC name 1,3-benzodioxol-5-yl (1R,3aR,4S,6aR)-4-(1,3-benzodioxol-5-yl) perhydrofuro[3,4-c]furan-1-yl ether; 1-(1,3-benzodioxol-5-yl)-4-(1,3-benzodioxol-5-yloxy) tetrahydrofuro[3,4-c]furan; 2-(1,3-benzodioxol-5-yl)-6-(1,3-benzodioxol-5-yloxy)-3,7- dioxabicyclo[3.3.0]octane Chemical Abstracts name [1S-(1α,3aα,4α,6aα)]-5-[4-(1,3-benzodioxol-5-yloxy) tetrahydro-1H,3H-furo[3,4-c]furan-1-yl]-1,3-benzodioxole CAS RN [526–07–8] Smiles code C1Oc2ccc(OC3OCC4C(OCC34)c5ccc6OCOc6c5)cc2O1 PHYSICAL CHEMISTRY: Mol. wt. 370.4 M.f. C 20 H 18 O 7 COMMERCIALISATION: History Synergistic activity with pyrethrum of sesame oil (from Sesamum indicum) reported by C. Eagleson (Soap Chem. Spec., 1942, 18(12), 125) and traced to sesasmolin by H. L. Haller et al. (J. Org. Chem., 1942, 7, 183; J. Econ. Entomol., 1942, 35, 247). simeton Herbicide NOMENCLATURE: Common name simeton (BSI, WSSA) IUPAC name N 2 ,N4-diethyl-6-methoxy-1,3,5-triazine-2,4-diamine; 2,4-bis(ethylamino)-6- methoxy-1,3,5-triazine Chemical Abstracts name N,N′-diethyl-6-methoxy-1,3,5-triazine-2,4-diamine CAS RN [673–04–1] Development codes G 30 044 Smiles code CCNc1nc(NCC)nc(OC)n1 PHYSICAL CHEMISTRY: Mol. wt. 197.2 M.f. C 8 H 15 N 5 O COMMERCIALISATION: History Herbicide developed by J. R. Geigy S.A. (later Ciba-Geigy AG). 482 The Pesticide Manual Sixteenth Edition © BCPC 2012 SMY 1500 SMY 1500 Herbicide NOMENCLATURE: IUPAC name 4-amino-6-tert-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one Chemical Abstracts name 4-amino-6-(1,1-dimethylethyl)-3-(ethylthio)- 1,2,4-triazin-5(4H)-one Other names ethiozin * (rejected common name proposal) CAS RN [64529–56–2] Development codes SMY 1500 (Bayer) Smiles code CCSc1nnc(c(=O)n1N)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 228.3 M.f. C 9 H 16 N 4 OS Form Colourless crystals. M.p. 96.4 °C V.p. 7.5 × 10 –3 mPa (20 °C) K ow logP = 2.08 Henry 5.04 × 10 –3 Pa m 3 mol –1 (calc.) Solubility In water 0.34 mg/l (20 °C). In dichloromethane >200, isopropanol 100–200, toluene 100–200 g/kg. COMMERCIALISATION: History Herbicide reported by H. Hack & L. Eue (Proc. 1985 Br. Crop Prot. Conf. - Weeds, 1, 35). Introduced in Israel (1989) by Bayer AG. APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor at the photosystem II receptor site. Uses Pre-emergence control of grasses (particularly Bromus spp.) and some broad- leaved weeds in cereals (mainly wheat) and tomatoes at 0.55–1.7 kg/ha. Formulation types WG . PRODUCTS: Discontinued products ‘Lektan’* (Bayer); ‘Tycor’* (Bayer). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for ratsc. 2000 mg/kg, micec. 1000, dogs >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. NOEL (2 y) for rats 25 mg/kg diet. ADI/RfD (EPA) 0.05 mg/kg b.w. [1990]. N N N O SCH 2 CH 3 (CH 3 ) 3 C NH 2 Supplementary Entries – Extended SN 106 279 483 SN 106 279 Herbicide NOMENCLATURE: IUPAC name methyl (R)-2-(7-(2-chloro-α,α,α-trifuoro-p-tolyloxy)-2-naphthyloxy) propionate Chemical Abstracts name methyl (R)-2-[[7-[2-chloro-4-(trifuoromethyl)phenoxy]-2- naphthalenyl]oxy]propanoate CAS RN [103055–61–4] Development codes SN 106 279 PHYSICAL CHEMISTRY: Mol. wt. 424.8 M.f. C 21 H 16 ClF 3 O 4 Form Tech. is a yellow liquid. V.p. 2.39 × 10 –3 mPa (25 °C) Solubility In water 0.7 mg/l. In ethanol and acetone 870, methanol 850 (g/l, 20 °C). COMMERCIALISATION: History Herbicide evaluated by Schering AG. Reported by F. Arndt et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1989, 1, 35). APPLICATIONS: Mode of action Taken up principally by plant leaves. Treated plants display diphenyl ether symptoms of root and shoot necrosis of meristems. Uses Post-emergence herbicide for control of broad-leaved weeds, such as Veronica spp., Viola spp., Lamium spp., in winter cereals, at 100–200 g/ha. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats >400 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats >>400 mg/kg. CH CH 3 O O F 3 C Cl CO 2 CH 3 484 The Pesticide Manual Sixteenth Edition © BCPC 2012 sodium (Z)-3-chloroacrylate SN 72129 Insecticide NOMENCLATURE: IUPAC name (E)-2-chlorobenzoyl(2,3-dihydro-4-phenyl-1,3-thiazol-2-ylidene)acetonitrile Chemical Abstracts name (E)-2-chloro-β-oxo-α-(4-phenyl-2(3H)-thiazolylidene) benzenepropanenitrile Other names thiapronil* (unadopted proposed common name) CAS RN [77768–58–2] unstated stereochemistry Development codes SN 72129 Smiles code Clc1ccccc1C(=O)C(=C2NC(=CS2)c3ccccc3)C#N PHYSICAL CHEMISTRY: Mol. wt. 338.8 M.f. C 18 H 11 ClN 2 OS Form Colourless crystals. M.p. 182–183 °C V.p. <1.3 × 10 –5 mPa (25 °C) Solubility In water 69 mg/l (room temperature). In acetone 0.015, methanol 4.2, isopropanol 1.9 (all in g/l). Stability Stable in acid and alkali. COMMERCIALISATION: History Insecticide reported by H. Joppien et al. (Proc. 10th Int. Congr. Plant Prot., 1983, 1, 392). Evaluated by Schering AG. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. sodium (Z)-3-chloroacrylate Plant growth regulator NOMENCLATURE: IUPAC name sodium (Z)-3-chloroacrylate Chemical Abstracts name sodium (Z)-3-chloro-2-propenoate Other names sodium cis-3-chloroacrylate CAS RN [4312–97–4] Development codes UC 20 299 Smiles code [Na+].[O-]C(=O)/C=C\Cl; without stereochemistry:[Na+].[O-]C(=O)C=CCl PHYSICAL CHEMISTRY: Mol. wt. 128.5 M.f. C 3 H 2 ClNaO 2 COMMERCIALISATION: History Herbicide reported by R. A. Herrett & A. N. Kurtz (Science, 1963, 141, 1192). Introduced as a defoliant by Union Carbide Corp. (later Rhône-Poulenc Ag.). C N S NH O Cl Supplementary Entries – Extended sodium fuoride 485 PRODUCTS: Discontinued products ‘Prep’* (Union Carbide). MAMMALIAN TOXICOLOGY: EC Classifcation Xn; R21/22 sodium fuoride Insecticide NOMENCLATURE: Common name fuorure de sodium (F-ISO, used in lieu of a common name); sodium fuoride (E-ISO, used in lieu of a common name) IUPAC name sodium fuoride Chemical Abstracts name sodium fuoride CAS RN [7681–49–4] EC no 231–667–8 Smiles code [F-].[Na+] PHYSICAL CHEMISTRY: Mol. wt. 42.0 M.f. FNa Form Colourless powder. M.p. 993 °C V.p. Negligible (room temperature) S.g./density 2.8 Solubility In water 42.2 g/l (18 °C). Slightly soluble in ethanol. COMMERCIALISATION: History Introduced in baits against insects in stores. APPLICATIONS: Mode of action Insecticide with stomach and contact action. Uses Used in insect baits and as a timber preservative. Phytotoxicity Highly phytotoxic. PRODUCTS: Discontinued products ‘Florocid’* (Allied). ANALYSIS: Product analysis is by determination of the fuorine content by titrimetric methods (AOAC Methods, 18th Ed., 921.04, 929.04, 933.03). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.951 (2003). MAMMALIAN TOXICOLOGY: Oral Highly toxic, the lowest oral lethal dose being 28–100 mg/kg for a range of vertebrates. Acute oral LD 50 for rats 180 mg/kg (Am. Ind. Hyg. Assoc. J., 1969, 30, 470). Toxicity Class WHO (a.i.) II EC Classifcation T; R25| Xi; R36/38| R32 NaF 486 The Pesticide Manual Sixteenth Edition © BCPC 2012 sodium fuoroacetate sodium fuoroacetate Rodenticide IRAC 26 NOMENCLATURE: Common name sodium fuoroacetate (E-ISO, accepted in lieu of a common name); fuoroacé(tate de sodium) (F-ISO, accepted in lieu of a common name); fuoroacetic acid (BSI, for parent acid) IUPAC name sodium fuoroacetate Chemical Abstracts name sodium fuoroacetate Other names Compound 1080 CAS RN [62–74–8] EC no 200–548–2 Smiles code [Na+].[O-]C(=O)CF PHYSICAL CHEMISTRY: Mol. wt. 100.0 M.f. C 2 H 2 FNaO 2 Form Colourless, hygroscopic powder. M.p. Decomposesc. 200 °C V.p. Non-volatile Solubility Very soluble in water. Almost insoluble in ethanol, acetone and petroleum oils. COMMERCIALISATION: History Rodenticidal properties reported by E. R. Kalmbeck (Science, 1945, 102, 232). APPLICATIONS: Biochemistry Inhibits aconitase in the tricarboxylic acid cycle. Uses Used in baits for control of rodents. In Australia, also used for control of wild rabbits, wild dogs and wild pigs. Formulation types CB . ANALYSIS: Product analysis is by conversion to lead chloride fuoride (AOAC Methods, 14th Ed., 6.019–6.062); sodium fuoride is a usual contaminant. For a qualitative determination of fuoroacetic acid in residues, see AOAC Methods, 18th Ed., 949.09; for quantitive determination by extraction, see ibid., 949.10, followed by fuorine determination, ibid., 944.08. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: PDS 16 (1975). ICSC.484 (1997). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for Rattus norvegicus 0.22 mg/kg (S. H. Dieke & C. P. Richter, U.S. Public Health Rep., 1946, 61, 672). Highly toxic to all other mammals (see Sodium monofuoroacetate). NOEL NOAEL (13 w) for rats 0.05 mg/kg b.w. daily (EPA RED). ADI/RfD (EPA) cRfD 0.00002 mg/kg b.w. [1993, 1995]. Toxicity Class WHO (a.i.) Ia. EC Classifcation T+; R26/27/28| N; R50 FCH 2 CO 2 Na Supplementary Entries – Extended sophamide 487 sodium selenate Insecticide NOMENCLATURE: IUPAC name sodium selenate Chemical Abstracts name disodium selenate CAS RN [13410–01–0] Smiles code [Na+].[Na+].[O-][Se](=O)(=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 188.9 M.f. Na 2 O 4 Se COMMERCIALISATION: History Introduced as an insecticide. sophamide Insecticide IRAC 1B NOMENCLATURE: Common name sophamide (BSI, E-ISO, (m) F-ISO) IUPAC name S-methoxymethylcarbamoylmethyl O,O-dimethyl phosphorodithioate; 2-dimethoxyphosphinothioylthio-N-methoxymethylacetamide Chemical Abstracts name S-[2-[(methoxymethyl)amino]-2-oxoethyl] O,O- dimethyl phosphorodithioate CAS RN [37032–15–8] Development codes MC-62 Smiles code COCNC(=O)CSP(=S)(OC)OC PHYSICAL CHEMISTRY: Mol. wt. 259.3 M.f. C 6 H 14 NO 4 PS 2 COMMERCIALISATION: History Insecticide evaluated by Murphy Chemical Co. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Formocarbam’* (Murphy). 488 The Pesticide Manual Sixteenth Edition © BCPC 2012 SSF-109 SSF-109 Fungicide NOMENCLATURE: Chemical Abstracts name (±)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl) cycloheptanol CAS RN [129586–32–9] Development codes SSF-109 (Shionogi) Smiles code OC1(CCCCCC1n2cncn2)c3ccc(Cl)cc3 PHYSICAL CHEMISTRY: Mol. wt. 291.8 M.f. C 15 H 18 ClN 3 O Form Colourless crystals. M.p. 128–129 °C K ow logP = 0.481 Solubility In water 125 mg/l (25 °C). COMMERCIALISATION: History Broad-spectrum fungicide introduced by Shionogi and Co. Ltd (whose agrochemical interests became Aventis CropScience Shionogi K.K. in 2001, became part of Bayer AG). APPLICATIONS: Biochemistry Inhibits ergosterol biosynthesis. Mode of action Systemic fungicide with preventive and curative action. Uses Broad-spectrum fungicide for control of Ascomycetes, Phycomycetes, Basidiomycetes, and Fungi Imperfecti on lettuce, cucumbers, wheat, oats, and rice. Particularly active against grey mould (Botrytis cinerea), including benzimidazole- resistant strains. ANALYSIS: Product by tlc or hplc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 153–214, mice 273 mg/kg. Other Negative in the Ames test and micronucleus test. ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 22.5, killifsh 10.9 mg/l. Daphnia LC 50 (3 h) for Daphnia pulex 100.5 mg/l. N N N HO Cl H N N N HO Cl H (1S,2S)- isomer (1R,2R)- isomer Supplementary Entries – Extended SSI-121 489 SSH-108 NOMENCLATURE: IUPAC name 2-difuoromethylthio-4,6-bis(isopropylamino)-1,3,5-triazine Chemical Abstracts name 6-[(difuoromethyl)thio]-N,N′-bis(1-methylethyl)-1,3,5- triazine-2,4-diamine CAS RN [103427–73–2] Development codes SSH-108 PHYSICAL CHEMISTRY: Mol. wt. 277.3 M.f. C 10 H 17 F 2 N 5 S APPLICATIONS: Uses In mixture with acetochlor for use in maize and other crops. SSI-121 Acaricide NOMENCLATURE: IUPAC name ((chlorobis(2-methyl-2-phenylpropyl)stannyl)methyl)trimethylsilane Chemical Abstracts name [[chlorobis(2-methyl-2-phenylpropyl)stannyl]methyl] trimethylsilane Other names bis(2-methyl-2-phenylpropyl)trimethylsilylmethyl stannyl chloride(II) CAS RN [108307–07–9] Development codes SSI-121 (Shionogi) Smiles code CC(C)(c1ccccc1)[Sn](Cl)(C[Si](C)(C)C)C(C)(C)c2ccccc2 PHYSICAL CHEMISTRY: Mol. wt. 507.8 M.f. C 24 H 37 ClSiSn COMMERCIALISATION: History Acaricide evaluated by Shionogi and Co., Ltd; discontinued in 1994. APPLICATIONS: Mode of action Contact acaricide. Uses Control of all stages of spider mites (including cyhexatin- and fenbutatin oxide-resistant strains) on apples, citrus fruit, tea, and other crops. Formulation types WP. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 15 (1980) is a general review of tin and tin compounds. N N N NHCH(CH 3 ) 2 (CH 3 ) 2 CHNH SCHF 2 (CH 3 ) 2 C Sn CH 2 Si(CH 3 ) 3 Cl C(CH 3 ) 2 CH 2 CH 2 490 The Pesticide Manual Sixteenth Edition © BCPC 2012 strychnine MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2000 mg/kg (Shibuya). Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg (Shibuya). strychnine Rodenticide NOMENCLATURE: Common name strychnine (BSI, E-ISO, F-ISO, accepted in lieu of a common name) IUPAC name strychnidin-10-one Chemical Abstracts name strychnidin-10-one CAS RN [57–24–9] EC no 200–319–7 Smiles code O=C1C[C@@H]2OCC=C3CN4CC[C@]56[C@@H]4C[C@@H]3[C@ @H]2[C@@H]6N1c7ccccc75;without stereochemistry:O=C1CC2OCC=C3CN4CCC56 C4CC3C2C6N1c7ccccc75 PHYSICAL CHEMISTRY: Mol. wt. 334.4 M.f. C 21 H 22 N 2 O 2 Form Colourless crystals. M.p. 270–280 °C (decomp.); >199 °C (sulfate) K ow logP = 4.0 (pH 7) Solubility In water 143 mg/l. In benzene 5.6, ethanol 6.7, chloroform 200 (all in g/l). Sparingly soluble in diethyl ether and petroleum spirit. Sulfate solubility in water 30 g/l (15 °C); soluble in ethanol. Stability Stable to light, and at pH 5–9. Strychnine is a base, and forms water-soluble salts with acids: the hydrochloride, with 1.5–2.0 moles of water of crystallisation which are lost at 110 °C; the sulfate, as pentahydrate, becoming anhydrous at 100 °C. Specifc rotation [α]D18 –139° (chloroform) pKa 8.26 COMMERCIALISATION: Production Produced by extracting seeds of Strychnos or Loganiaceae spp. History The physiological properties of the alkaloids in extracts of Strychnos (Loganiaceae) species have long been known, strychnine being the most important. Seeds of Strychnos nux- vomica were used as a rat poison in Germany in the late 17th century. Strychnine was frst isolated in pure form from St. Ignatius beans (Strychnos ignatii) in 1818 (Pest Control Agents from Natural Products). APPLICATIONS: Biochemistry Antagonist to the neurotransmitter glycine, acting principally on the spinal cord. Mode of action Rodenticide absorbed mainly by the intestine. Uses Used N O O N H H H H H Supplementary Entries – Extended sulfallate 491 (as strychnine sulfate) for control of moles, squirrels, rabbits, gophers, mice and other small mammals, and also for control of sparrows, pigeons and other bird pests. Rats are somewhat resistant, as they normally avoid the bait. Formulation types CB; RB . ANALYSIS: Product analysis by acid-base titration (AOAC Methods, 18th Ed., 920.211) or by spectrophotometry (ibid., 962.22). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: ICSC.197 (2000). EU Status (1107/2009) Not approved, 2004/129/EC. MAMMALIAN TOXICOLOGY: Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. ADI/RfD (EPA) cRfD 0.0003 mg/kg b.w. [1988]. Other Lethal dose: for rats 1–30 mg/kg; for bearsc. 0.5 mg/kg; for man 30–60 mg/kg. Toxicity Class WHO (a.i.) Ib. EC Classifcation T+; R27/28| N; R50, R53 (base): T+; R26/28| N; R50, R53 (salts) ECOTOXICOLOGY: Birds Acute oral LD 50 for starlings <5.0 mg sulfate/kg. Dietary LC 50 for bobwhite quailc. 4000, mallard ducksc. 200 ppm. ENVIRONMENTAL FATE: Animals Rapidly absorbed by gastro-intestinal tract but not through the skin. Distribution, metabolism to several non-toxic polar products, and excretion, are rapid. Only 5–20% of unchanged alkaloid is excreted in the urine; the major metabolites were the 21,22-epoxide and strychnine N-oxide. Soil/Environment Immobile in soil; degraded microbially. sulfallate Herbicide NOMENCLATURE: Common name CDEC (WSSA); sulfallate (BSI, E-ISO, (m) F-ISO) IUPAC name 2-chloroallyl diethyldithiocarbamate Chemical Abstracts name 2-chloro-2-propenyl diethylcarbamodithioate CAS RN [95–06–7] EC no 202–388–9 Development codes CP 4742 (Monsanto) Smiles code CCN(CC)C(=S)SCC(=C)Cl PHYSICAL CHEMISTRY: Mol. wt. 223.8 M.f. C 8 H 14 ClNS 2 Form Amber oil. B.p. 128 °C /1 mmHg V.p. 293 mPa (20 °C) S.g./density 1.088 (25 °C) Solubility In water 92 mg/l (25 °C). Soluble in most organic solvents. Stability Hydrolysed by alkali; DT 50 47 d (pH 5), 30 d (pH 8). COMMERCIALISATION: History Herbicide introduced by the Monsanto Co. Patents US 2744898, US 2919182. 492 The Pesticide Manual Sixteenth Edition © BCPC 2012 sulfoxide APPLICATIONS: Biochemistry Inhibits lipid metabolism. Mode of action Systemic, selective herbicide, readily absorbed by plant roots but not by foliage. Uses As a pre-em. herbicide (3–6 kg/ha) on a wide range of vegetable crops controlling annual weeds, but not established or vegetatively propagating perennials. Formulation types EC; GR . PRODUCTS: Discontinued products ‘Vegadex’* (Monsanto). ANALYSIS: Product analysis is by glc. Residues may be determined by glc (Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 704; see also Pestic. Anal. Man., I, 302). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: IARC 30 (1983). MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 850 mg/kg. Skin and eye It is somewhat irritant to skin and eyes. Toxicity Class WHO (a.i.) II EC Classifcation R45| Xn; R22| N; R50, R53 ENVIRONMENTAL FATE: Soil/Environment Persists in soil for 21–42 d. sulfoxide Insecticide synergist NOMENCLATURE: Common name sulfoxide (ESA) IUPAC name 2-(1,3-benzodioxol-5-yl)-1-methylethyl octyl sulfoxide; 1-methyl-2-(3,4- methylenedioxyphenyl)ethyl octyl sulfoxide Chemical Abstracts name 5-[2-(octylsulfnyl)propyl]-1,3-benzodioxole CAS RN [120–62–7] Smiles code CCCCCCCCS(=O)C(C)Cc1ccc2OCOc2c1 PHYSICAL CHEMISTRY: Composition Tech. is ≥88%. Mol. wt. 324.5 M.f. C 18 H 28 O 3 S Form Tech. is a brown liquid with a mild odour. B.p. Decomposes without boiling. S.g./density 1.06–1.09 (25 °C, tech.) Solubility Practically insoluble in water. Miscible with most organic solvents; in petroleum oils 20–25 g/kg. COMMERCIALISATION: History Synergist for pyrethroid insecticides reported by M. E. Synerholm et al. (Contrib. Boyce Thompson Inst., 1947, 15, 35). Introduced by S. B. Penick & Co. Patents US 2486445 (to Boyce Thompson Institute). PRODUCTS: Discontinued products ‘Sulfocide’* (Penick). Supplementary Entries – Extended sulprofos 493 ANALYSIS: Product analysis is by uv spectroscopy at 288 nm, after isolation by steam distilllation (WHO Insecticides, 30 Rev. 1,p. 170). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 2000–2500 mg/kg. Toxicity Class WHO (a.i.) III sulglycapin Herbicide NOMENCLATURE: Common name sulglycapin (BSI, E-ISO, (m) F-ISO) IUPAC name azepan-1-ylcarbonylmethyl methylsulfamate Chemical Abstracts name 2-(hexahydro-1H-azepin-1-yl)-2-oxoethyl methylsulfamate CAS RN [51068–60–1] Development codes BAS 461H; BAS 46 100H (both BASF) Smiles code CNS(=O)(=O)OCC(=O)N1CCCCCC1 PHYSICAL CHEMISTRY: Mol. wt. 250.3 M.f. C 9 H 18 N 2 O 4 S COMMERCIALISATION: History Herbicide reported by E. Eysell et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1976, 2, 709). Evaluated by BASF AG. sulprofos Insecticide IRAC 1B NOMENCLATURE: Common name sulprofos (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name O-ethyl O-4-(methylthio)phenyl S-propyl phosphorodithioate Chemical Abstracts name O-ethyl O-[4-(methylthio)phenyl] S-propyl phosphorodithioate CAS RN [35400–43–2] Development codes NTN 9306; BAY 123234 (both Bayer) Smiles code CCCSP(=S)(OCC)Oc1ccc(SC)cc1 PHYSICAL CHEMISTRY: Mol. wt. 322.4 M.f. C 12 H 19 O 2 PS 3 Form Colourless oil, with a mercaptan-like odour; (tech., tan liquid). M.p. –15 °C (tech.) B.p. 125 °C /1 Pa V.p. 0.084 mPa (20 °C); 0.16 mPa (25 °C) O P S OCH 2 CH 3 SCH 2 CH 2 CH 3 CH 3 S 494 The Pesticide Manual Sixteenth Edition © BCPC 2012 sulprofos K ow logP = 5.48 Henry 8.74 × 10-2 Pa m 3 mol –1 (20 °C, calc.) S.g./density 1.20 (20 °C) Solubility In water 0.31 mg/l (20 °C). In isopropanol 400–600, dichloromethane, hexane, toluene >1200 (all in g/l, 20 °C). Stability Hydrolysis in buffer systems, DT 50 (22 °C) 26 d (pH 4), 151 d (pH 7), 51 d (pH 9). Photodegraded in water and on soil surfaces. For flms in sunlight, 50% decomposition occurs in <2 days. F.p. 64 °C COMMERCIALISATION: History Insecticide reported by G. Zoebelein (Proc. Conf. Pest Control, 4th, Cairo, 1978, p. 456). Introduced by Bayer AG. Patents NL 6508899 (1965) (to Bayer) Manufacturers Bayer Corp. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide with contact and stomach action. Uses Control of Lepidoptera, Thysanoptera, Heliothis spp., and other insects in cotton, soya beans, tobacco, vegetables, and tomatoes. Formulation types EC; UL . PRODUCTS: Discontinued products ‘Bolstar’* (Bayer CropScience); ‘Helothion’* (Bayer). ANALYSIS: Product analysis by glc with FID (AOAC Methods, 18th Ed., 980.12). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). ICSC.248 (1995). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 304, female rats 176, male and female micec. 1700 mg/ kg. Skin and eye Acute percutaneous LD 50 for male rats 5491, female rats 1064 mg/kg. Not irritating to skin; mild irritant to eyes (rabbits). Not a skin sensitiser. Inhalation LC 50 (4 h) for male and female rats >4130 μg/l air. NOEL (2 y) for dogs 10 mg/kg diet (0.25 mg/ kg b.w.), rats 6, mice 2.5. ADI/RfD (EPA) 0.003 mg/kg b.w. [1986]. Toxicity Class WHO (a.i.) II EPA (formulation) II EC Classifcation (T; R25| Xn; R21) ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 47 mg/kg. Dietary LC 50 (5 d) for bobwhite quail 99 mg/kg diet. Fish LC 50 (96 h) for bluegill sunfsh 11–14, rainbow trout 23–38 mg/l. Daphnia LC 50 (48 h) 0.83–1 μg/l. Algae ErC50 for Selenastrum capricornutum 64 mg/l. ENVIRONMENTAL FATE: Animals In rats, following oral administration,c. 92% is eliminated within 24 h. The main degradation products are the oxygen-analogue, phenol, sulprofos sulfoxide and sulprofos sulfone, and the corresponding oxygen-analogues and phenols. Plants The major metabolites are sulprofos sulfoxide and sulprofos sulfone. The corresponding phenols and oxygen-analogues are minor degradation products. Soil/Environment The adsorption of sulprofos in various soil types occurred rapidly; the compound is highly adsorbed. DT 50 in the range of some days to several weeks, depending on the soil types. The major metabolites are sulprofos sulfoxide and sulprofos sulfone. Supplementary Entries – Extended swep 495 sultropen Fungicide NOMENCLATURE: Common name sultropè(ne) ((m) F-ISO); sultropen (BSI, E-ISO) IUPAC name 2,4-dinitrophenyl pentyl sulfone Chemical Abstracts name 2,4-dinitro-1-(pentylsulfonyl)benzene CAS RN [963–22–4] Development codes RD 7901; BTS 7901 Smiles code CCCCCS(=O)(=O)c1ccc(cc1[N+](=O)[O-])[N+](=O)[O-] PHYSICAL CHEMISTRY: Mol. wt. 302.3 M.f. C 11 H 14 N 2 O 6 S COMMERCIALISATION: History Fungicide evaluated by Boots Co., Ltd (later Schering Agrochemicals). swep Herbicide NOMENCLATURE: Common name swep (ANSI, WSSA); MCC (JMAF) IUPAC name methyl 3,4-dichlorocarbanilate Chemical Abstracts name methyl (3,4-dichlorophenyl)carbamate CAS RN [1918–18–9] Development codes FMC 2995 Smiles code COC(=O)Nc1ccc(Cl)c(Cl)c1 PHYSICAL CHEMISTRY: Mol. wt. 220.1 M.f. C 8 H 7 Cl 2 NO 2 COMMERCIALISATION: History Herbicide reported by H. R. Hudgins (Proc. South. Weed Control Conf., 1963, 16, 118). Introduced by FMC Corp. ANALYSIS: In water, by lc with uv detection, see AOAC Methods, 18th Ed., 992.14. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22 496 The Pesticide Manual Sixteenth Edition © BCPC 2012 SYP-Z048 SYP-Z048 Fungicide NOMENCLATURE: Chemical Abstracts name 3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine Other names dingjunezuo CAS RN [847749–37–5] Development codes SYP-Z048 (Shenyang Research) PHYSICAL CHEMISTRY: Mol. wt. 288.8 M.f. C 16 H 17 ClN 2 O Form Light yellow sticky oil. Solubility Insoluble in water. Very soluble in acetone, ethyl acetate and chloroform. COMMERCIALISATION: History Discovered by Shenyang Research Institute of Chemical Industry in 1996 and registered in China in 2002. APPLICATIONS: Mode of action Broad spectrum systemic fungicide with protective and curative properties. Uses For control of tomato grey mould, apple spot leaf drop, peanut brown spot, cucumber scab, wheat root rot and grape white rot. Formulation types EC. PRODUCTS: Other products ‘Jun Si Qi’ (Shenyang Research). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 2000, female rats 1710 mg/kg. Skin and eye Acute dermal LD 50 for rabbits >2000 mg/kg. Other Negative in Ames test. O N CH 3 CH 3 N Cl Supplementary Entries – Extended SYP-Z071 497 SYP-Z071 Fungicide FRAC 11, C3; QoI; strobilurin type: methoxyacrylate NOMENCLATURE: IUPAC name methyl 2-{2-[3-(4-chlorophenyl)-1-methylallylideneaminooxymethyl] phenyl}-3-methoxyacrylate Other names enestroburin; enestrobin CAS RN [750643–57–3] Development codes SYP-Z071 Smiles code COC=C(C(=O)OC)c1ccccc1CON=C(C)C=Cc2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 399.9 M.f. C 22 H 22 ClNO 4 Form White crystals; (tech. is a pale yellow oil). Solubility Insoluble in water. Very soluble in acetone, ether and chloroform. COMMERCIALISATION: History Discovered by Shenyang Research Institute of Chemical Industry in 1997 and reported by L. X. Zhang et al. (Proc. BCPC. Int. Congr., Glasgow, 2003, 1, 93). APPLICATIONS: Biochemistry Quinone outside Inhibitor. Respiratory electron transport inhibitor. Acts by inhibiting cytochrome pathway (Complex III) between cytochrome b and cytochrome c1, at the ubiquinol oxidising site. Mode of action Protective, curative translaminar and systemic fungicide, with secondary insecticidal activity. Uses Provides broad-spectrum disease control, for example of cucumber downy mildew (Pseudoperonospora cubensis), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber grey mould (Botrytis cinerea) and wheat powdery mildew (Blumeria graminis). Also active against Lepidoptera. Formulation types EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 926, female rats 749 mg/kg. Skin and eye Acute percutaneous LD 50 for male and female rabbits >2000 mg/kg. Slight eye irritation; no skin irritation (rabbits). Other Negative in Ames test. Cl N CH 3 O O CH 3 O O CH 3 498 The Pesticide Manual Sixteenth Edition © BCPC 2012 2,4,5-T 2,4,5-T Herbicide Esters include: 2,4,5-T-butotyl (the 2-butoxyethyl), 2,4,5-T-butyl, 2,4,5-T-isoctyl (the iso- octyl), and 2,4,5-T-butometyl (the 2-butoxy-1-methylethyl). NOMENCLATURE: Common name 2,4,5-T (BSI, E-ISO, (m) F-ISO, WSSA, JMAF); 2,4,5-T (also used by JMAF for the butotyl ester) IUPAC name (2,4,5-trichlorophenoxy)acetic acid Chemical Abstracts name (2,4,5-trichlorophenoxy)acetic acid CAS RN [93–76–5] 2,4,5-T; [3813–14–7] 2,4,5-T-trolamine; [2008–46–0] 2,4,5-T-triethylammonium; [25168– 15–4] 2,4,5-T-isoctyl EC no 202–273–3 Smiles code OC(=O)COc1cc(Cl)c(Cl)cc1Cl PHYSICAL CHEMISTRY: Composition Tech. is 94%. Mol. wt. 255.5; 367.7 (2,4,5-T-isoctyl) M.f. C 8 H 5 Cl 3 O 3 ; C16H21Cl3O3 (2,4,5-T-isoctyl) Form Colourless crystals. M.p. 154-155 °C; 113-115 °C (tris(2-hydroxyethyl)ammonium salt); solidifes 20 °C (tech., butyl ester) V.p. 7 × 10 –4 mPa (25 °C) K ow logP = 2.0 (ARS PPD, unstated pH) Henry 1.19 × 10 –6 Pa m 3 mol –1 (calc.) S.g./density 1.80 (20 °C) Solubility In water 150 mg/l (25 °C). In methanol 496, ethanol 548.2, diethyl ether 234.3, toluene 7.32, xylene 6.08, heptane 0.4 (all in g/l, 25 °C). The alkali-metal and amine salts are readily soluble in water, but insoluble in petroleum oils. The esters are practically insoluble in water, but soluble in petroleum oils. Stability Stable in aqueous solution at pH 5–9. pKa 2.85 (J. Agr. & Food Chem., 26, 189 (1978)) COMMERCIALISATION: Production Manufactured by condensation of sodium chloroacetate with sodium 2,4,5-trichlorophenoxide. At high temperatures the action of alkali on 2,4,5-trichlorophenol can produce some 2,3,7,8-tetrachlorodibenzo-p-dioxin. History Herbicide reported by C. L. Hamner & H. B. Tukey (Science, 1944, 100, 154). Introduced by Amchem Products Inc. (later Rhône-Poulenc Agrochimie). APPLICATIONS: Biochemistry Similar to that of 2,4-D. Mode of action Selective systemic herbicide with hormone-like action, absorbed by the roots, bark, and foliage, and translocated through the phloem. Uses Control of woody weeds, brush, and undergrowth in grassland and non-crop land. Control of tree shoots and undergrowth in forestry. Treatment of tree stumps to prevent regrowth. Amine formulations were used for weed control in rice. Phytotoxicity Phytotoxic to almost all broad-leaved crops, and particularly cotton, tomatoes, ornamentals, grapes, and fruit trees. Formulation types EC; SL . Compatibility Mixing with solutions of heavy-metal salts, e.g. copper sulfate, can lead to focculation. Cl Cl Cl OCH 2 CO 2 H Supplementary Entries – Extended 2,4,5-T 499 PRODUCTS: Discontinued products ‘Sylvoxone 850’* (isoctyl ester) (Sopra); ‘Weedone’* (Rhône- Poulenc). ANALYSIS: Product analysis by hplc (AOAC Methods, 18th Ed., 980.08; J. Assoc. Off. Anal. Chem., 1980, 63, 379), by hplc, or glc or titration (CIPAC Handbook, 1985, 1C, 2220), by glc of a suitable ester (CIPAC Handbook, 1985, 1C, 2072, 2257; 1994, F, 292–319), or by an epinasty determination (AOAC Methods, 18th Ed., 960.10). Free phenol impurity determined by hplc (CIPAC Handbook, 1994, F, 362). Estimation of 2,3,7,8-tetrachlorodibenzo-p-dioxin content has been studied (J. W. Edmunds et al., Pestic. Sci., 1973, 4, 101; P. G. Baker et al., ibid., 1981, 12, 297; CIPAC Handbook, 1994, F, 352; ibid., 1985, C, 2284). Residues determined by glc of a suitable ester (Pestic. Anal. Man., 1979, 1, 201-D; W. Specht & M. Tillkes, Fresenius’ Z. Anal. Chem., 1980, 301, 300; 1981, 4307, 257; Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 702; H. Løkke & P. Odgaard, Pestic. Sci., 1981, 12, 375; H. E. Munro, ibid., 1977, 8, 157). In drinking water by conversion to methyl ester with diazomethane, then glc with ECD (AOAC Methods, 18th Ed., 992.32). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: JMPR Evaln. 33 (1979), 37 (1981). PDS 13 (1975). IARC 41 (1986); Suppl. 7 (1987). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: IARC Class 2B Oral Acute oral LD 50 for rats 300–1700 mg/kg (depending on vehicle and rat strain); for mice 389–1380, dogs 100 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. NOEL In 2-y feeding trials no effect observed in rats receiving 30 mg/kg diet; nor in 90 d trials in beagle dogs at 60 mg/kg diet. ADI/RfD (JMPR) 0.03 mg/kg b.w. [1981], for 2,4,5-T containing not more than 0.01 mg tetrachlorodibenzodioxin (TCDD)/ kg; (EPA) cRfD 0.01 mg/kg b.w. [1989]. Water GV 0.009 mg/l. Other A contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), produced foetal deaths in hamsters at 0.0091 mg/kg and it causes serious acne in man. Later methods of manufacture of 2,4,5-T limited the amount of the contaminant to <0.01 mg/kg 2,4,5-T. Toxicity Class WHO (a.i.) II EC Classifcation Xn; R22| Xi; R36/37/38| N; R50, R53 (for acid, salts or esters) PIC Yes. ECOTOXICOLOGY: Birds Acute oral LC 50 (8 d) for bobwhite quail 2776 mg/kg diet; for ducks >4650 mg/kg diet. Fish LC 50 (96 h) for rainbow trout 350, carp 355 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In mammals, following oral administration, 50% is eliminated in the urine within 23 h. There is no accumulation. Plants Degradation in plants is similar to that for 2,4-D. This involves cleavage of the acetic acid moiety, ring hydroxylation of the 2,4,5-trichlorophenol so formed, and presumably ring opening and degradation. Soil/ Environment In soil, degradation occurs more slowly than for 2,4-D. 500 The Pesticide Manual Sixteenth Edition © BCPC 2012 tar oils tar oils Fungicide, herbicide, insecticide NOMENCLATURE: CAS RN [65996–82–9], coal tar oils; [8002–29–7] tar oils (naphthalene oils, derived from wood tar); different numbers apply to tar oils from other sources PHYSICAL CHEMISTRY: Composition Tar oils consist mainly of aromatic hydrocarbons, but contain components soluble in aqueous alkali: the ‘phenols’ or ‘tar acids’; and nitrogenous bases soluble in dilute mineral acids: ‘tar bases’. They are produced by the distillation of tars resulting from the high-temperature carbonisation of coal and of coke oven and blast furnace tars. Form Brown to black liquids. B.p. Tar oils are the FRACtion boiling from 230 °C upwards. S.g./density 1.05–1.11 (15 °C) Solubility Insoluble in water. Soluble in most organic solvents and in dimethyl sulfate. COMMERCIALISATION: Production Tar oils are produced by the distillation of tars resulting from the high- temperature carbonisation of coal and of coke oven and blast furnace tars. History Although they have been used for wood preservation since 1890, the introduction of the formulated products known as tar oil washes for crop protection, using the heavy creosote and anthracene oil ranges, dates fromc. 1920. APPLICATIONS: Uses Control of overwintering stages (particularly eggs) of many insects, e.g. aphids, suckers, moths, Mealybugs and scale insects, and overwintering diseases on dormant pome, stone, cane and bush fruit, and grape vines. Moss and lichen are also controlled. Also used as a hop defoliant, and as a game repellent in forestry. Phytotoxicity Extremely phytotoxic, and so must only be used during the dormant season. Formulation types EC; Emulsion. PRODUCTS: Discontinued products ‘Clean-Up’* (Miracle). ANALYSIS: Product analysis is by standard methods (MAFF Ref. Bk., 1958, No. 1, p. 81). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, 2004/129/EC. MAMMALIAN TOXICOLOGY: Skin and eye Irritating to skin, eyes and respiratory system. May cause dermatitis, especially in sunlight. EC Classifcation Tar oils are classifed as R45 ECOTOXICOLOGY: Fish Toxic to fsh. Supplementary Entries – Extended 2,4,5-TB 501 tazimcarb Insecticide, molluscicide NOMENCLATURE: Common name tazimcarbe ((m) F-ISO); tazimcarb (BSI, E-ISO) IUPAC name N-methyl-1-(3,5,5-trimethyl-4-oxo-1,3-thiazolidin-2-ylideneamino-oxy) formamide; 3,5,5-trimethyl-2-methylcarbamoyloxyimino-1,3-thiazolidin-4-one Chemical Abstracts name 3,5,5-trimethyl-2,4-thiazolidinedione 2-[O-[(methylamino) carbonyl]oxime]; formerly 2-[[[(aminocarbonyl)oxy]methyl]imino]-3,5,5- trimethyl-4-thiazolidinone CAS RN [40085–57–2], formerly [62113–03–5] Development codes PP505 Smiles code CNC(=O)ON=C1SC(C)(C)C(=O)N1C PHYSICAL CHEMISTRY: Mol. wt. 231.3 M.f. C 8 H 13 N 3 O 3 S COMMERCIALISATION: History Insecticide and molluscicide evaluated by ICI Agrochemicals. APPLICATIONS: Biochemistry Cholinesterase inhibitor. 2,4,5-TB Herbicide NOMENCLATURE: Common name 2,4,5-TB (BSI, E-ISO, (m) F-ISO, WSSA) IUPAC name 4-(2,4,5-trichlorophenoxy)butyric acid Chemical Abstracts name 4-(2,4,5-trichlorophenoxy)butanoic acid CAS RN [93–80–1] Smiles code OC(=O)CCCOc1cc(Cl)c(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 283.5 M.f. C 10 H 9 Cl 3 O 3 COMMERCIALISATION: History Herbicide. 502 The Pesticide Manual Sixteenth Edition © BCPC 2012 2,3,6-TBA 2,3,6-TBA Herbicide HRAC O WSSA 4; benzoic acid (auxin) NOMENCLATURE: Common name 2,3,6-TBA (BSI, E-ISO, (m) F-ISO, WSSA); acide trichlorobenzoique (optional alternative in France); TCBA (JMAF) IUPAC name 2,3,6-trichlorobenzoic acid Chemical Abstracts name 2,3,6-trichlorobenzoic acid CAS RN [50–31–7]; [2078– 42–4] 2,3,6-TBA-sodium EC no 200–026–4 Development codes HC-1281 (Heyden) Smiles code OC(=O)c1c(Cl)ccc(Cl)c1Cl PHYSICAL CHEMISTRY: Composition Tech. grade isc. 60% 2,3,6-TBA. Mol. wt. 225.5 M.f. C 7 H 3 Cl 3 O 2 Form Colourless crystals; (tech., colourless to buff, crystalline powder). M.p. 125–126 °C (pure acid);c. 80–100 °C (tech.) B.p. Decomposes on distillation V.p. Very low at room temperature; 3.2 Pa (100 °C) Solubility In water 7.7 g/l (22 °C). Readily soluble in common organic solvents, e.g. acetone 60.7, benzene 23.8, chloroform 23.7, ethanol 63.7, methanol 71.7, xylene 21.0 (all in g/100 ml). Sodium salt, in water 440 g/kg (25 °C). Stability Stable to light, and to temperatures up to 60 °C. COMMERCIALISATION: History Herbicide reported by H. J. Miller (Weeds, 1952, 1, 185). Introduced by the Heyden Chemical Corp. and later by E. I. du Pont de Nemours & Co. (who now neither manufacture nor market it), and currently available in mixtures with other herbicides. Patents US 2848470 (1958); US 3081162 (1963) APPLICATIONS: Biochemistry Auxin type. Mode of action Systemic growth-regulator herbicide with hormone-like action, absorbed by the leaves and roots. Uses Used post-emergence, in combinations with other growth regulator herbicides, in cereals and grass seed crops to control broad-leaved annual and perennial weeds, including Bilderdykia convolvulus, Galium aparine, Polygonum aviculare, P. persicaria, Chamomilla and Matricaria spp. Compatibility Mixtures with fertilisers are not recommended. PRODUCTS: Discontinued products ‘Trysben’* (dimethylammonium salt) (DuPont); Discontinued mixtures ‘Benzabor’* (+ borax) (US Borax). Cl CO 2 H Cl Cl Supplementary Entries – Extended TDE 503 ANALYSIS: Product and salt analysis by titration or by glc (CIPAC Handbook, 1985, 1C, 2225; ibid., 2257; ibid., 1994, F, 292–319); in mixture with MCPA, by titration or by glc of a derivative (ibid., 1985, 1C, 2148). Residues determined by glc of a suitable derivative (J. J. Kirkland & H. L. Pease, J. Agric. Food Chem., 1964, 12, 468). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1500, mice 1000, guinea pigs >1500, rabbits 600 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg. NOEL In 64–69 d feeding trials, rats receiving 10 000 mg/kg diet suffered a minor disturbance of water metabolism, no trace of which was apparent at 1000 mg/kg diet. It is largely excreted unchanged in the urine. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R22| N; R51, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for hens >1500 mg/kg. Fish Threshold value for toxic activity 100–150 mg/l for perch and 300 mg/l for roach. One of several determining factors is the content of the second, more toxic, 2,4,5- isomer in the active ingredient. Bees Not toxic to bees. ENVIRONMENTAL FATE: Animals In mammals, excretion is mainly as the unchanged form in the urine. Soil/Environment Very slow degradation in soil. A stable protein complex may possibly be formed. TDE Insecticide NOMENCLATURE: Common name TDE (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane Chemical Abstracts name 1,1′-(2,2-dichloroethylidene)bis[4-chlorobenzene] Other names DDD CAS RN [72–54–8] Development codes Me-1700 Smiles code ClC(Cl)C(c1ccc(Cl)cc1)c2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 320.0 M.f. C 14 H 10 Cl 4 B.p. 193 °C (Agchem. Desk Ref.) Solubility In water 0.05 ppm (25 °C) (Residue Reviews, 103, 1 (1988)) Stability Stable to hydrolysis; DT 50 28 y (pH 7, 25 °C) (Agchem. Desk Ref.) COMMERCIALISATION: History Insecticide reported by P. Läuger et al. (Helv. Chim. Acta, 1944, 27, 892). Introduced by Rohm & Haas Co. (found in nature as a degradation product of DDT). 504 The Pesticide Manual Sixteenth Edition © BCPC 2012 tebutam APPLICATIONS: Mode of action Contact, ingested insecticide. PRODUCTS: Discontinued products ‘Rhothane’* (Rohm & Haas). ANALYSIS: See Pestic. Anal. Man., I, 303, 502. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O tebutam Herbicide HRAC K1 WSSA 3; benzamide (mi) NOMENCLATURE: Common name tebutam (BSI, E-ISO); té(butame) ((m) F-ISO); butam (ANSI, WSSA); no name (Japan) IUPAC name N-benzyl-N-isopropylpivalamide Chemical Abstracts name 2,2-dimethyl-N-(1-methylethyl)-N-(phenylmethyl) propanamide CAS RN [35256–85–0] EC no 252–470–3 Development codes GPC-5544 (Gulf); Ro 14–9480/000 (Roche); CGA 39625 (Ciba- Geigy) Smiles code CC(C)N(Cc1ccccc1)C(=O)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 233.4 M.f. C 15 H 23 NO Form Light brown liquid. B.p. 95–97 °C /0.1 mmHg V.p.c. 89 mPa (25 °C) K ow logP = 3 Henry 1.5 × 10-2 Pa m 3 mol –1 (calc.) S.g./density 0.975 (20 °C) Solubility In water 0.79 g/l (pH 7, 20 °C). Readily soluble in organic solvents, e.g. acetone, hexane, methanol, toluene, chloroform >500 g/l (25 °C). Stability Chemically stable under normal storage conditions. Thermally stable at temperatures below the boiling point. Stable to light. Stable to hydrolysis at pH 5, 7 and 9 (all at 25 °C). F.p. >80 °C (with 2% toluene) COMMERCIALISATION: History Herbicide reported by R. A. Schwartzbeck (Proc. Br. Crop Prot. Conf. – Weeds, 1976, 2, 739). Introduced by Gulf Oil Chemicals Co. and later acquired by Dr R. Maag Ltd (became Syngenta AG). Patents US 3974218; US 3707366 (to Gulf) Manufacturers Syngenta CH 2 N CH(CH 3 ) 2 C C(CH 3 ) 3 O Supplementary Entries – Extended tecoram 505 APPLICATIONS: Biochemistry Microtubule assembly inhibition. Mode of action Selective herbicide, acting by inhibition of weed germination and also through root uptake. Uses Pre- emergence control of annual grasses, volunteer cereals and broad-leaved weeds in oilseed rape and brassicas, at 2.8–3.6 kg/ha. Phytotoxicity A large number of crops are susceptible, including cereals, maize, carrots, fax, onions, garlic, lettuce, melons, sorghum, spinach, and sugar beet. Formulation types EC. PRODUCTS: Discontinued products ‘Colzor’* (Novartis); ‘Comodor’* (Novartis). ANALYSIS: Product analysis by hplc. Residues determined by glc with FID or by hplc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for albino rats 6210, guinea pigs 2025 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and albino rabbits >2000 mg/kg. A slight irritant to the eyes and skin of rabbits. Inhalation LC 50 for rats >2.18 mg/l air. There was no adverse effect when albino rats were exposed to an aerosol (66% vol. mixture of tech. product and acetone). NOEL (2 y) for rats 600, mice 3000 ppm. ADI/RfD (BfR) 0.3 mg/kg b.w. [1990]. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Dietary LC 50 (8 d) for mallard ducks and bobwhite quail >5000 mg/kg. Fish LC 50 (96 h) for rainbow trout 23, bluegill sunfsh 19, moonfsh 18.7 mg/l. Algae LC 50 (96 h) for Scenedesmus subspicatus 82 mg/l. Bees Acute oral LD 50 100 μg/bee. ENVIRONMENTAL FATE: Animals In rats, following oral administration, rapidly excreted in the urine and faeces. Plants In plants, tebutam is rapidly metabolised. Soil/Environment Bound by the organic matter of soil; DT 50 c. 2 mo. tecoram Fungicide NOMENCLATURE: Common name tecoram (BSI) IUPAC name N′,N′,N′′′,N′′′-tetramethyl-N,N′′-ethylenedi(thiuram disulfde) Chemical Abstracts name N,N,N′,N′-tetramethyl-4,9-dithioxo-2,3,10,11-tetrathia-5,8- diazadodecanedithioamide CAS RN [5836–23–7] Smiles code CN(C)C(=S)SSC(=S)NCCNC(=S)SSC(=S)N(C)C 506 The Pesticide Manual Sixteenth Edition © BCPC 2012 TEPP PHYSICAL CHEMISTRY: Mol. wt. 450.8 M.f. C 10 H 18 N 4 S 8 COMMERCIALISATION: History Fungicide evaluated by Aagrunol N.V. PRODUCTS: Discontinued products ‘Azosan’* (Aagrunol). TEPP Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name TEPP (BSI, E-ISO, (m) F-ISO, ESA, JMAF); ethyl pyrophosphate (BAN) IUPAC name tetraethyl pyrophosphate Chemical Abstracts name tetraethyl diphosphate Other names TEP CAS RN [107– 49–3] EC no 203–495–3 Smiles code CCOP(=O)(OCC)OP(=O)(OCC)OCC PHYSICAL CHEMISTRY: Mol. wt. 290.2 M.f. C 8 H 20 O 7 P 2 Form Colourless hygroscopic liquid; (tech. is a dark amber- coloured mobile liquid). B.p. 124 °C /1 mmHg V.p. 21 mPa (20 °C) S.g./density 1.185 (20 °C);c. 1.2 (25 °C, tech.) Solubility Miscible with water and most organic solvents; sparingly soluble in petroleum oils. Stability Rapidly hydrolysed by water, DT 50 6.8 h (pH 7, 25 °C). Decomposes at 170 °C with the formation of ethylene. COMMERCIALISATION: History Aphicide discovered in 1938 by G. Schrader & H. Kükenthal (cited by G. Schrader, Phosphorsäure-Ester). In 1943, I. G. Farbenindustrie AG introduced a derivative then thought to be hexaethyl tetraphosphate (known as HETP) but since shown to contain TEPP as the main insecticidal component. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic acaricide and aphicide. Uses Acaricide and aphicide with a very brief persistence. Formulation types AE . PRODUCTS: Discontinued products ‘Nifos T’* (Monsanto); ‘Vapotone’* (Chevron). ANALYSIS: Product analysis by selective hydrolysis (CIPAC Handbook, 1970, 1, 667; AOAC Methods, 18th Ed., 949.06). Residues determined by glc (J. Crossley, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 471). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). Supplementary Entries – Extended terallethrin 507 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1.12 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats 2.4 mg/kg. Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R27/28| N; R50 ENVIRONMENTAL FATE: Animals It is rapidly metabolised by animals. terallethrin Insecticide IRAC 3 NOMENCLATURE: Common name terallethrin (BSI, E-ISO); té(rallé) ((f) F-ISO) IUPAC name (RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl 2,2,3,3-tetramethylcyclopropanecarboxylate Chemical Abstracts name (±)-2-methyl-4-oxo-3-(2-propenyl)-2-cyclopenten- 1-yl 2,2,3,3-tetramethylcyclopropanecarboxylate CAS RN [15589–31–8] unstated stereochemistry Development codes M-108 Smiles code CC1=C(CC=C)C(=O)CC1OC(=O)C2C(C)(C)C2(C)C PHYSICAL CHEMISTRY: Mol. wt. 276.4 M.f. C 17 H 24 O 3 Form Light yellow oily liquid. V.p. 27 mPa (20 °C) Solubility Insoluble in water. Soluble in organic solvents. Stability Unstable to light and to alkali. COMMERCIALISATION: History Insecticide introduced by Sumitomo Chemical Co., Ltd. Manufacturers Jiangsu Yangnong APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. Uses Public health fumigant insecticide used for control of housefies and cockroaches. ANALYSIS: Analysis of pyrethroids reviewed by E. Papadopoulou-Mourkidou in Comp. Anal. Profles. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 174–224 mg/kg. CH 3 CH 3 CH 3 C CH 3 H O O CH 3 CH 2 CH CH 2 O 508 The Pesticide Manual Sixteenth Edition © BCPC 2012 terbuchlor terbucarb Herbicide NOMENCLATURE: Common name MBPMC (JMAF); terbucarb (BSI, E-ISO); terbucarbe ((m) F-ISO); terbutol (WSSA) IUPAC name 2,6-di-tert-butyl-p-tolyl methylcarbamate Chemical Abstracts name 2,6-bis(1,1-dimethylethyl)-4-methylphenyl methylcarbamate CAS RN [1918–11–2] Development codes Hercules 9573 Smiles code CNC(=O)Oc1c(cc(C)cc1C(C)(C)C)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 277.4 M.f. C 17 H 27 NO 2 COMMERCIALISATION: History Herbicide reported by A. H. Haubein & J. R. Hansen (J. Agric. Food Chem., 1965, 13, 555). Introduced by Hercules Inc. (later Nor-Am.). PRODUCTS: Discontinued products ‘Azak’* (Hercules). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O terbuchlor Herbicide NOMENCLATURE: Common name terbuchlor (BSI, E-ISO, ANSI, WSSA); terbuchlore ((m) F-ISO) IUPAC name N-butoxymethyl-6′-tert-butyl-2-chloroacet-o-toluidide Chemical Abstracts name N-(butoxymethyl)-2-chloro-N-[2-(1,1-dimethylethyl)-6- methylphenyl]acetamide CAS RN [4212–93–5] Development codes MON 0358; CP 46 358 Smiles code CCCCOCN(C(=O)CCl)c1c(C)cccc1C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 325.9 M.f. C 18 H 28 ClNO 2 COMMERCIALISATION: History Herbicide evaluated by Monsanto Co. Supplementary Entries – Extended tetcyclacis 509 tetcyclacis Plant growth regulator NOMENCLATURE: Common name tetcyclacis (BSI, E-ISO, (m) F-ISO) IUPAC name rel-(1R,2R,6S,7R,8R,11S)-5-(4-chlorophenyl)-3,4,5,9,10-penta- azatetracyclo[5.4.1.02,6.08,11]dodeca-3,9-diene Chemical Abstracts name (3aα,4β,4aα,6aα,7β,7aα)-1-(4-chlorophenyl)-3a,4,4a,6a,7,7a- hexahydro-4,7-methano-1H-[1,2]diazeto[3,4-f]benzotriazole CAS RN [77788–21–7] Development codes BAS 106W (BASF) Smiles code Clc1ccc(cc1)N 2 N=NC3C4CC(C5N=NC54)C32 PHYSICAL CHEMISTRY: Mol. wt. 273.7 M.f. C 13 H 12 ClN 5 Form Colourless crystalline solid. M.p. 190 °C (decomp.) Solubility In water 3.7 mg/kg (20 °C). In chloroform 42, ethanol 2 (both in g/kg, 20 °C). Stability Decomposed by sunlight and concentrated acid. COMMERCIALISATION: History Plant growth regulator reported by J. Jung et al. (Z. Acker-Pfanzenbau, 1980, 149, 128). Introduced by BASF AG. Patents DE 2615878; GB 1573161; US 4189434 APPLICATIONS: Biochemistry Gibberellin and sterol biosynthesis inhibitor. Mode of action Plant growth retardant. Uses It was used for improvement of rice seedlings. Treated seedlings are more compact and shorter than untreated ones and they show enhanced rooting and tillering capacity after transplanting into the feld. Formulation types SP. PRODUCTS: Discontinued products ‘Ken byo’* (BASF). ANALYSIS: Product analysis is by hplc with uv detection. Residues may be determined by glc with ECD of a derivative. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 261 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >4640 mg/kg. ECOTOXICOLOGY: Algae EC 50 (cell volume) for Chlorella fusca 5.2 μ;mol/l (Pestic. Sci. (1996) 47, 337). 510 The Pesticide Manual Sixteenth Edition © BCPC 2012 tetrachlorvinphos tetrachlorothiophene Nematicide NOMENCLATURE: IUPAC name tetrachlorothiophene (I) Chemical Abstracts name (I) Other names TCTP CAS RN [6012–97–1] Development codes TD-183 Smiles code Clc1sc(Cl)c(Cl)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 221.9 M.f. C 4 Cl 4 S COMMERCIALISATION: History Nematicide developed by Pennwalt Corp. PRODUCTS: Discontinued products ‘Penphene’* (Pennwalt). tetrachlorvinphos Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name tetrachlorvinphos (BSI, E-ISO, (m) F-ISO); stirofos (ESA); CVMP (JMAF) IUPAC name (Z)-2-chloro-1-(2,4,5-trichlorophenyl)vinyl dimethyl phosphate Chemical Abstracts name (Z)-2-chloro-1-(2,4,5-trichlorophenyl)ethenyl dimethyl phosphate CAS RN [22248–79–9] tetrachlorvinphos; [22350–76–1] the analogous (E)- isomer; [961–11–5] mixed (Z)- + (E)- isomers Development codes SD 8447 (Shell) Smiles code COP(=O)(OC)O/C(=C\Cl)/c1cc(Cl)c(Cl)cc1Cl;without stereochemistry:COP(=O)(OC)OC(=CCl)c1cc(Cl)c(Cl)cc1Cl PHYSICAL CHEMISTRY: Composition Tech. grade is typically 98% pure. Mol. wt. 366.0 M.f. C 10 H 9 Cl 4 O 4 P Form Tech. is an off-white crystalline solid. M.p. 94–97 °C V.p. 0.0056 mPa (20 °C) Henry 1.86 × 10 –4 Pa m 3 mol –1 (calc.) Solubility In water 11 mg/l (20 °C). In acetone <200, chloroform, dichloromethane 400, xylene <150 (all in g/kg, 20 °C). Stability Stable <100 °C; slowly hydrolysed (50 °C), DT 50 54 d (pH 3), 44 d (pH 7), 80 h (pH 10.5). O P(OCH 3 ) 2 O Cl Cl C Cl C Cl H (Z)- isomer Supplementary Entries – Extended tetrachlorvinphos 511 COMMERCIALISATION: History Insecticide reported by R. R. Whetsone et al. (J. Agric. Food Chem., 1966, 14, 352). Introduced by Shell Chemical Company, USA (later DuPont Agricultural Products, who transferred rights to Fermenta Animal Health Co., which became Boehringer Ingelheim Vetmedica, Inc., and to Hartz Mountain for pet uses). Patents US 3102842 Manufacturers Shanghai MCC APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide and acaricide with contact and stomach action. Uses A selective insecticide controlling Lepidoptera and Diptera in fruit; and Lepidoptera in cotton, maize, rice, tobacco and vegetables. With certain exceptions, not highly active against Hemiptera and other sucking pests and, because of rapid breakdown, is not effective against soil-dwelling pests. It is used against Muscidae in dairies and in livestock barns, against certain ectoparasites on poultry, and against pests of stored products. Also used against insects that damage forests and pasture. Phytotoxicity Russetting may occur on Golden Delicious apples under certain conditions. Formulation types DP; EC; SC. WP. Compatibility Incompatible with dodine and with alkaline materials. PRODUCTS: Discontinued products ‘Appex’* (Shionogi); ‘Debantic’* (ISK Biosciences); ‘Gardcide’* (Cyanamid); ‘Gardona’* (crop protection use) (BASF); ‘Rabon’* (DuPont); ‘Rabond’* (Cyanamid). ANALYSIS: Product analysis by glc with FID; details available from BASF. Residues of tetrachlorvinphos and its major metabolites in plants determined by glc (Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 297; K. I. Beynon & A. N. Wright, J. Sci. Food Agric., 1969, 20, 250; K. I. Beynon et al., Pestic. Sci., 1970, 1, 250, 254, 259). See also Pestic. Anal. Man., II, 180.252, 186.950. In drinking water by glc with NPD (AOAC Methods, 18th Ed., 991.07). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). IARC 30 (1983). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: IARC Class 3 Oral Acute oral LD 50 for rats 4000–5000, mice 2500–5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2500 mg/kg. NOEL NOAEL for rats 4.23 mg/kg b.w. (EPA RED); NOEL (2 y) for rats 125 mg/kg diet, for dogs 200 mg/kg diet. Reproduction studies on rats receiving 1000 mg/kg diet showed no adverse effects. ADI/RfD (EPA) aRfD 0.067, cRfD 0.0423 mg/kg b.w. [2006]. Toxicity Class WHO (a.i.) U EPA (formulation) III ECOTOXICOLOGY: Birds Acute oral LD 50 for Chukar partridges and mallard ducks >2000 mg/kg, for various other birds 1500–2600 mg/kg. Fish LC 50 (24 h) for fve different species 0.3–6.0 mg/l. Bees Toxic to bees. 512 The Pesticide Manual Sixteenth Edition © BCPC 2012 O,O,O′,O′-tetrapropyl dithiopyrophosphate ENVIRONMENTAL FATE: Animals In mammals, rapid metabolism occurs, with elimination of the metabolites within a few days. Metabolites found in the urine of dogs and rats include 2,4,5-trichlorophenylethanediol glucuronide, further glucuronic acid derivatives, 2,4,5-trichloromandelic acid, and 2-chloro-1-(2,4,5-trichlorophenyl)vinylmethyl hydrogen phosphate. No signifcant residues of tetrachlorvinphos or its metabolites are found in milk or tissues of exposed animals. Soil/Environment For a review on metabolism and breakdown in plants, animals and soil, see K. I. Beynon et al., Residue Rev., 1973, 47, 55. tetrafuron Herbicide NOMENCLATURE: Common name tetrafuron (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name 1,1-dimethyl-3-[3-(1,1,2,2-tetrafuoroethoxy)phenyl]urea Chemical Abstracts name N,N-dimethyl-N′-[3-(1,1,2,2-tetrafuoroethoxy) phenyl]urea CAS RN [27954–37–6], formerly [34766–29–5] and [36510–94–8] Development codes Hoe 2991 Smiles code CN(C)C(=O)Nc1cccc(OC(F)(F)C(F)F)c1 PHYSICAL CHEMISTRY: Mol. wt. 280.2 M.f. C 11 H 12 F 4 N 2 O 2 COMMERCIALISATION: History Herbicide evaluated by Hoechst AG. O,O,O′,O′-tetrapropyl dithiopyrophosphate Insecticide IRAC 1B NOMENCLATURE: IUPAC name O,O,O′,O′-tetrapropyl dithiopyrophosphate Chemical Abstracts name tetrapropyl thiodiphosphate; thiodiphosphoric acid ([(HO)2P(S)]2O) tetrapropyl ester Other names NPD CAS RN [3244–90–4] EC no 221–817–0 Development codes ASP-51 (Stauffer) Smiles code CCCOP(=S)(OCCC)OP(=S)(OCCC)OCCC PHYSICAL CHEMISTRY: Composition Tech. is 93–96%. Mol. wt. 378.4 M.f. C 12 H 28 O 5 P 2 S 2 Form Tech. is a straw to amber-coloured liquid, with a faint aromatic odour. B.p.c. 170 °C /1 mmHg V.p. c. 13 mPa (25 °C) S.g./density 1.119–1.123 (20 °C) Solubility In water 30 mg/l (20 °C). Miscible with acetone, ethanol, kerosene, 4-methylpentan-2-one, xylene. Stability Stable <100 °C. DT 50 32 d (pH 7 buffer, 40 °C). Supplementary Entries – Extended tetrasul 513 COMMERCIALISATION: History Insecticide reported by A. D. F. Toy (J. Am. Chem. Soc., 1951, 73, 4670). Introduced by Stauffer Chemical Co. (later ICI Americas). Patents US 2663722 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide. Uses Insecticide particularly effective at 8.6. kg/ha for the control of Blissus leucopterus in turf. Formulation types EC; GR . PRODUCTS: Discontinued products ‘Aspon’* (Stauffer); ‘Sod’* (Chevron). ANALYSIS: Product analysis by glc with FID (R. D. Mills & M. Yuan, Anal. Methods Pestic. Plant Growth Regul., 1984, 13, 149). Residues in soil and turf determined by glc (idem, ibid.). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male albino rats 2800, female rats 740 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Mildly irritating to skin and non-irritating to eyes (rabbits). Other In 90 d feeding trials at sublethal rates, rats showed some depression of red blood cell cholinesterase. EC Classifcation Xn; R21/22 ENVIRONMENTAL FATE: Soil/Environment Persistent in soil. tetrasul Acaricide NOMENCLATURE: Common name tetradisul (Canada); diphenylsulphide (JMAF); tetrasul (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name 4-chlorophenyl 2,4,5-trichlorophenyl sulfde Chemical Abstracts name 1,2,4-trichloro-5-[4-(chlorophenyl)thio]benzene CAS RN [2227–13–6] Development codes V-101 (N. V. Philips-Roxane) Smiles code Clc1ccc(Sc2cc(Cl)c(Cl)cc2Cl)cc1 PHYSICAL CHEMISTRY: Composition Tech. is ≥77.5%. Mol. wt. 324.1 M.f. C 12 H 6 Cl 4 S Form Tech. is a cream to yellow-brown solid. M.p. 88.4–88.6 °C; (tech., 75–85 °C) V.p. 0.10 mPa (20 °C) Henry 1.0 8 Pa m 3 mol –1 (calc.) Solubility In water 0.03 mg/l (20 °C). In 1,2-dichloroethane 274, ethanol 20, xylene 400 (all for tech., in g/l, 20 °C). Stability Stable at ambient temperature in the dark; it is slowly oxidised via the corresponding sulphoxide to tetradifon under prolonged exposure to sunlight. No conversion after 30 min at 90 °C in a methanolic potassium hydroxide solution; <2% decomposition after 7 d at pH 6 as a 25 mg/l suspension in water. 514 The Pesticide Manual Sixteenth Edition © BCPC 2012 thiadifuor COMMERCIALISATION: History Acaricide reported by J. Meltzer & F. C. Dietvoorts (Proc. Int. Congr. Crop Prot., 4th, 1957, 1, 669). Introduced by N.V. Philips-Roxane (later Uniroyal Chemical Co., Inc.). Patents NL 94329; US 3054719 APPLICATIONS: Mode of action Contact acaricide. Uses For the control of various phytophagous mites which hibernate in the winter egg form. It is necessary to apply it when the winter eggs were about to hatch. It was recommended for use on cucumber, bush fruit, top fruit and grapes at 36 g/100 l. Formulation types WP. PRODUCTS: Discontinued products ‘Animert V101’* (DuPont). ANALYSIS: Product analysis by glc (L. R. Mitchell, J. Assoc. Off. Anal. Chem., 1976, 59, 209). Residues determined by glc (idem, ibid.; AOAC Methods, 18th Ed., 976.23). See also Pestic. Anal. Man., I, 303. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 8250, female rats 6810, male and female mice 5010, male guinea pigs 8250, female guinea pigs 8800 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. NOEL (2 y) for rats 10 mg/kg diet. In 90 d feeding trials, beagle-dogs tolerated 200 mg/kg diet. In a 3-generation study on rats, NOEL 20 mg/kg diet Toxicity Class WHO (a.i.) U thiadifuor Fungicide NOMENCLATURE: Common name thiadifuor (BSI, E-ISO, (m) F-ISO) IUPAC name 3-(4-chlorophenyl)-N 2 -methyl-N4,N5-bis(trifuoromethyl)-1,3-thiazolidine- 2,4,5-triylidenetriamine Chemical Abstracts name N,N′-[3-(4-chlorophenyl)-2-(methylimino)-4,5- thiazolidinediylidene]bis[1,1,1-trifuoromethanamine] CAS RN [80228–93–9] Development codes SLJ 4027a Smiles code CN=C1SC(=NC(F)(F)F)C(=NC(F)(F)F)N1c2ccc(Cl)cc2 PHYSICAL CHEMISTRY: Mol. wt. 353.3 M.f. C 12 H 7 F 6 N 4 S COMMERCIALISATION: History Fungicide introduced by Bayer AG. Supplementary Entries – Extended thiazafuron 515 thiazafuron Herbicide NOMENCLATURE: Common name thiazafuron (BSI, E-ISO, (m) F-ISO); thiazfuron (Canada) IUPAC name 1,3-dimethyl-1-(5-trifuoromethyl-1,3,4-thiadiazol-2-yl)urea Chemical Abstracts name N,N′-dimethyl-N-[5-(trifuoromethyl)-1,3,4-thiadiazol-2-yl] urea CAS RN [25366–23–8] EC no 246–901–4 Development codes GS 29 696 Smiles code CNC(=O)N(C)c1nnc(s1)C(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 240.2 M.f. C 6 H 7 F 3 N 4 OS Form Colourless crystals. M.p. 136–137 °C V.p. 0.27 mPa (20 °C) K ow logP = 1.82 Henry 3.09 × 10 –5 Pa m 3 mol –1 (calc.) S.g./density 1.6 (20 °C) Solubility In water 2.1 g/l (20 °C). In ethanol 300, methanol 257, n-octanol 60, DMF 600, xylene <50, benzene 12, hexane dichloromethane 146 (all in g/kg, 20 °C). Stability No signifcant hydrolysis in 28 d at pH 1, pH 5 or pH 7. COMMERCIALISATION: History Herbicide reported by G. Müller et al. (C. R. Journ. Etud. Herbic. Conf. COLUMA, 7th, 1973, p. 32). Introduced by Ciba-Geigy AG. Patents BE 725984; GB 1254468 APPLICATIONS: Biochemistry Photosynthetic electron transport inhibitor. Mode of action Non- selective soil-herbicide, absorbed principally by the roots. Uses Control of most annual and perennial grasses and broad-leaved weeds, in addition to woody plants such as shrubs and bushes, on uncultivated land, industrial land, railway tracks, etc. Applied either pre- emergence or early post-emergence at 2–8 kg/ha in moist and temperate and 6–12 kg/ha in warm and dry regions. Formulation types GR; WP. PRODUCTS: Discontinued products ‘Erbotan’* (Ciba-Geigy). ANALYSIS: Product analysis by hplc. Residues determined by glc with FPD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 278, mice 630 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2150 mg/kg. Slight irritant to eyes, but non-irritant to skin (rabbits). Inhalation LC 50 of 80% formulation for rats >0.35 mg/l. NOEL (90 d) for rats 160 mg/kg diet (11 mg/kg daily); (105 d) for dogs 250 mg/kg diet (8 mg/kg daily). N N S F 3 C N CH 3 CONHCH 3 516 The Pesticide Manual Sixteenth Edition © BCPC 2012 thicyofen Toxicity Class WHO (a.i.) II EC Classifcation Xn; R22| N; R50, R53 ECOTOXICOLOGY: Birds Slightly toxic to birds. Fish LC 50 (96 h) for rainbow trout 82, bluegill sunfsh and crucian carp >100 mg/l. Bees Not toxic to bees. ENVIRONMENTAL FATE: Soil/Environment Degraded in soils, DT 50 50–200 d. thicrofos Insecticide IRAC 1B NOMENCLATURE: Common name thicrofos (BSI, E-ISO, (m) F-ISO) IUPAC name S-(6-chloro-3,4-dihydro-2H-1-benzothi-in-4-yl) O,O-diethyl phosphorothioate Chemical Abstracts name S-(6-chloro-3,4-dihydro-2H-1-benzothiopyran-4-yl) O,O-diethyl phosphorothioate CAS RN [41219–32–3] unstated stereochemistry Development codes Hoe 20 906 Smiles code CCOP(=O)(OCC)SC1CCSc2ccc(Cl)cc12 PHYSICAL CHEMISTRY: Mol. wt. 352.8 M.f. C 13 H 18 ClO 3 PS 2 COMMERCIALISATION: History Insecticide evaluated by Hoechst AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor. thicyofen Fungicide NOMENCLATURE: Common name thicyofè(ne) ((m) F-ISO); thicyofen (BSI, E-ISO) IUPAC name (±)-3-chloro-5-ethylsulfnylthiophene-2,4-dicarbonitrile Chemical Abstracts name (±)-3-chloro-5-(ethylsulfnyl)-2,4-thiophenedicarbonitrile CAS RN [116170–30–0] unstated stereochemistry Development codes PH 51–07; DU S CH 3 CH 2 S CN Cl CN O Supplementary Entries – Extended thidiazimin 517 510 311 (Duphar) Smiles code CCS(=O)c1sc(C#N)c(Cl)c1C#N PHYSICAL CHEMISTRY: Mol. wt. 244.7 M.f. C 8 H 5 ClN 2 OS 2 Form Solid. M.p. 130 °C V.p. <1 mPa (20 °C) K ow logP = 2.54 Henry <1.02 × 10 –3 Pa m 3 mol –1 (calc.) Solubility In water 240 mg/l (20 °C). COMMERCIALISATION: History Fungicide reported by T. W. Hofman et al. (Proc. 1990 Br. Crop Prot. Conf. - Pests Dis., 2, 431). Introduced by Duphar B.V. (later Uniroyal Chemical Co., Inc.). APPLICATIONS: Biochemistry Multi-site inhibitor. Uses Non-systemic seed treatment for control of Fusarium and Pythium spp., Pyrenophora graminea, and Tilletia caries in cereals, maize and cotton. Also used as a soil treatment for control of Pythium spp. in fower bulbs. Formulation types SC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 395, female rats 368 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Other Non-mutagenic in in vitro tests. Toxicity Class WHO (a.i.) II ECOTOXICOLOGY: Birds Acute oral LD 50 for bobwhite quail 216 mg/kg. Dietary LC 50 for bobwhite quail and mallard ducks >5620 mg/kg. ENVIRONMENTAL FATE: Soil/Environment Rapidly degraded in soil, DT 50 <30 d. thidiazimin Herbicide HRAC E WSSA 14; thiadiazole NOMENCLATURE: Common name thidiazimin (BSI, E-ISO); thidiazimine ((f) F-ISO) IUPAC name (Z)-6-(6,7-dihydro-6,6-dimethyl-3H,5H-pyrrolo[2,1-c][1,2,4]thiadiazol-3- ylideneamino)-7-fuoro-4-(2-propynyl)-2H-1,4-benzoxazin-3(4H)-one Chemical Abstracts name 6-[(6,7-dihydro-6,6-dimethyl-3H,5H-pyrrolo[2,1-c][1,2,4] thiadiazol-3-ylidene)amino]-7-fuoro-4-(2-propynyl)-2H-1,4-benzoxazin-3(4H)-one CAS RN [123249–43–4] Development codes SN 124 085 Smiles code CC1(C) Cc2nsc(=Nc3cc4N(CC#C)C(=O)COc4cc3F)n2C1 PHYSICAL CHEMISTRY: Mol. wt. 372.4 M.f. C 18 H 17 FN 4 O 2 S Form Colourless crystals. M.p. 158 °C V.p. 5.0 × 10-8 mPa (25 °C) K ow logP = 3.0 (pH 7) Henry 2.82 × 10 –9 Pa m 3 mol –1 (calc.) Solubility In water (6.6 ± 0.5) × 10 –3 g/l (pH 7, 25 °C). pKa 2.6±0.1 (conjugate acid) 518 The Pesticide Manual Sixteenth Edition © BCPC 2012 thiocarboxime COMMERCIALISATION: History Herbicide reported by R. Weiler et al. (Proc. Br. Crop Prot. Conf. – Weeds, 1993, 1, 29). Evaluated by Schering AG. APPLICATIONS: Biochemistry Protoporphyrinogen oxidase inhibitor. Mode of action Contact herbicide with rapid action. Uses Post-emergence control of broad-leaved weeds in winter cereals, particularly effective against Lamium purpureum, Veronica hederifolia, Veronica persica and Viola arvensis. Application rates were 20–40 g/ha. Formulation types SC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >4000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >>5000 mg/kg. No skin or eye irritancy (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 for rats >4.89 mg/l. Other Non-teratogenic and non-genotoxic. ECOTOXICOLOGY: Birds Low toxicity to birds. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 30–70 d, depending on soil type. Soil adsorption coeffcient (K oc ) 700–1200 ml/g. thiocarboxime Acaricide, insecticide NOMENCLATURE: Common name thiocarboxime (BSI, E-ISO, (f) F-ISO) IUPAC name 3-[1-(methylcarbamoyloxyimino)ethylthio]propiononitrile Chemical Abstracts name 2-cyanoethyl N-[[(methylamino)carbonyl]oxy] ethanimidothioate CAS RN [25171–63–5] Development codes WL 21 959; SD 17250 Smiles code CNC(=O)ON=C(C)SCCC#N PHYSICAL CHEMISTRY: Mol. wt. 201.2 M.f. C 7 H 11 N 3 O 2 S COMMERCIALISATION: History Insecticide and acaricide evaluated by Shell Research Ltd. APPLICATIONS: Biochemistry Cholinesterase inhibitor. PRODUCTS: Discontinued products ‘Talcord’* (Shell). Supplementary Entries – Extended 2-thiocyanatoethyl laurate 519 thiochlorfenphim Fungicide NOMENCLATURE: Common name thiochlorfenphim (BSI, E-ISO); thiochlorphenphim ((f) F-ISO); thiochlorphenphime (France) IUPAC name N-(4-chlorophenylthiomethyl)phthalimide Chemical Abstracts name 2-[[(4-chlorophenyl)thio]methyl]-1H-isoindole-1,3(2H)- dione CAS RN [19378–58–6] Development codes BAY 66 109; SRA 3208 Smiles code Clc1ccc(SCN 2 C(=O)c3ccccc3C2=O)cc1 PHYSICAL CHEMISTRY: Mol. wt. 303.8 M.f. C 15 H 10 ClNO 2 S COMMERCIALISATION: History Fungicide evaluated by Bayer AG. 2-thiocyanatoethyl laurate Insecticide NOMENCLATURE: IUPAC name 2-thiocyanatoethyl laurate Chemical Abstracts name 2-thiocyanatoethyl dodecanoate CAS RN [301–11–1] Smiles code CCCCCCCCCCCC(=O)OCCSC#N PHYSICAL CHEMISTRY: Mol. wt. 285.5 M.f. C 15 H 27 NO 2 S COMMERCIALISATION: History Insecticide developed by Rohm & Haas Co. PRODUCTS: Discontinued products ‘Lethane 60’* (Rohm & Haas). 520 The Pesticide Manual Sixteenth Edition © BCPC 2012 thiofanox thiofanox Acaricide, insecticide IRAC 1A; oxime carbamate NOMENCLATURE: Common name thiofanocarb (Republic of South Africa); thiofanox (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name 3,3-dimethyl-1-methylthiobutanone O-methylcarbamoyloxime; 1-(2,2-dimethyl-1-methylthiomethylpropylideneamino-oxy)-N-methylformamide Chemical Abstracts name 3,3-dimethyl-1-(methylthio)-2-butanone O-[(methylamino) carbonyl]oxime CAS RN [39196–18–4] EC no 254–346–4 Development codes DS 15 647 (Diamond Shamrock) Smiles code CNC(=O)ON=C(CSC)C(C)(C)C PHYSICAL CHEMISTRY: Mol. wt. 218.3 M.f. C 9 H 18 N 2 O 2 S Form Colourless solid, with a pungent odour. M.p. 56.5– 57.5 °C V.p. 22.6 mPa (25 °C) Solubility In water 5.2 g/l (22 °C). Readily soluble in chlorinated and aromatic hydrocarbons, ketones and non-polar solvents. Slightly soluble in aliphatic hydrocarbons. Stability Stable to heat under normal storage conditions. Relatively stable to hydrolysis at pH 5–9 (under 30 °C). Decomposed by strong acids and alkalis. COMMERCIALISATION: History Insecticide reported by R. L. Schauer (Proc. Br. Insectic. Fungic. Conf., 7th, 1973, 2, 713). Relationship between chemical structure and biological activity of analogues reported by T. A. Magee & L. E. Limpel (J. Agric. Food Chem., 1977, 25, 1376). Introduced by Diamond Shamrock Chemical Co. Later sold to Rhône-Poulenc Agrochimie (now Bayer AG). Manufacturers Bayer CropScience APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide. Uses Soil application for control of black bean aphids, beet leaf miners, Flea beetles and pygmy mangold beetles on beet; fea beetles on rape; aphids, capsids, fea beetles, colorado beetle and leafhoppers on potatoes; aphids, midges, fea beetles, soil- inhabiting larvae and spider mites on cotton; aphids and spider mites in foriculture, etc. Applied at rates in the range 0.4–3 kg/ha. Formulation types GR . PRODUCTS: Discontinued products ‘Benelux’* (ISK Biotech); ‘Dacamox’* (Bayer CropScience). CH 3 NH C N C C(CH 3 ) 3 CH 2 SCH 3 O O Supplementary Entries – Extended thionazin 521 ANALYSIS: Residues, which are likely to include thiofanox, its sulfoxide and sulfone, are oxidised to the sulfone, which is determined by glc (W. T. Chin, J. Agric. Food Chem., 1975, 23, 963; M. B. Szalkowski et al., J. Chromatogr., 1976, 128, 426). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for albino rats 8.5 mg/kg. Skin and eye Acute percutaneous LD 50 for albino rabbits 39 mg/kg. NOEL (90 d) for rats and beagle dogs 1 mg/kg daily. Clinical symptoms of reversible cholinesterase inhibition at 4.0 mg/kg daily, lasting for 3–4 hours. Weight gain of rats receiving 100 mg/kg diet was not affected. ADI/RfD (EPA) 0.0003 mg/ kg b.w. [1988]. Toxicity Class WHO (a.i.) Ib EPA (formulation) I EC Classifcation T+; R27/28| N; R50, R53 ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks 109, bobwhite quail 43 mg/kg. Fish LC 50 (96 h) for rainbow trout 0.13, bluegill sunfsh 0.33 mg/l. Bees Not toxic to bees when used as directed. ENVIRONMENTAL FATE: Animals Metabolism of carbamate insecticides is reviewed (M. Cool & C. K. Jankowski in Insecticides). Plants Metabolism in plants is the same as in soil. The duration of activity following absorption through the roots is at least 8 weeks. Soil/Environment In soil, the methylthio group is rapidly oxidised to the sulfoxide and, further, to the sulfone. Further degradation occurs to water-soluble metabolites. thionazin Insecticide, nematicide IRAC 1B NOMENCLATURE: Common name thionazin (BSI, E-ISO); thionazine ((m) F-ISO) IUPAC name O,O-diethyl O-pyrazin-2-yl phosphorothioate Chemical Abstracts name O,O-diethyl O-pyrazinyl phosphorothioate CAS RN [297–97–2] EC no 206–049–6 Development codes Experimental Nematicide 18 133 (Cyanamid) Smiles code CCOP(=S)(OCC)Oc1cnccn1 PHYSICAL CHEMISTRY: Composition Tech. isc. 90%. Mol. wt. 248.2 M.f. C 8 H 13 N 2 O 3 PS Form Colourless to pale yellow liquid; (tech. is a dark brown liquid). M.p. -1.67 °C V.p. 400 mPa (30 °C) Henryc. 8.71 × 10-2 Pa m 3 mol –1 (calc.) S.g./density 1.207 (25 °C); tech. 1.204–1.210 522 The Pesticide Manual Sixteenth Edition © BCPC 2012 thiophanate (25 °C) Solubility In water 1.14 g/l (27 °C). Miscible with most organic solvents. Stability Readily hydrolysed by alkali (pH >9). COMMERCIALISATION: History Nematicide introduced by American Cyanamid Co. Patents US 2918468; US 2938831; US 3091614 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Uses Soil insecticide and nematicide effective against a number of plant-parasitic as well as free-living nematodes, including those attacking buds, bulbs, leaves and roots, as well as against soil dwelling pests such as root maggots and symphylids and foliar insects such as aphids and leaf miners. When incorporated in mushroom compost at spawning it is effective against mushroom fies. It is of short persistence. Formulation types EC; GR . PRODUCTS: Discontinued products ‘Bulb Dip’* (Neals); ‘Cynem’* (Cyanamid); ‘Nemafos’* (Cyanamid); ‘Zinophos’* (Cyanamid). ANALYSIS: Product analysis is by hydrolysis with fuorimetric determination of the sodium salt of pyrazin-2-ol (U. Kiigemagi et al., J. Agric. Food Chem., 1963, 11, 293). Residues may be determined by glc (D. R. Coahran, Bull. Environ. Contam. Toxicol., 1966, 1, 208). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 12 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rats 11 mg/kg. NOEL In feeding trials, rats receiving 25 mg/kg diet for 30 d and then 50 mg/kg diet for 60 d showed a moderate depression in growth rate, but no abnormal behavioural reactions. ADI/RfD (EPA) 0.00005 mg/kg b.w. [1987]. Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R27/28 ECOTOXICOLOGY: Birds LC 50 (5 d) for bobwhite quail 65, pheasants 72 mg/kg diet. Fish LC 50 (48 h) for harlequin fsh 0.09 mg (as 480 g/l EC)/l. Bees LD 50 (topical) for honeybees 42 ng/l. thiophanate Anthelmintic, fungicide FRAC 1, B1 NOMENCLATURE: Common name thiophanate (BSI, E-ISO, (m) F-ISO, JMAF, BAN); thiophanate-é(thyl) ((m) France) Supplementary Entries – Extended thioquinox 523 IUPAC name diethyl 4,4′-(o-phenylene)bis(3-thioallophanate) Chemical Abstracts name diethyl [1,2-phenylenebis(iminocarbonothioyl)] bis[carbamate] CAS RN [23564–06–9] Development codes NF 35 (Nippon Soda) Smiles code CCOC(=O)NC(=S)Nc1ccccc1NC(=S)NC(=O)OCC PHYSICAL CHEMISTRY: Mol. wt. 370.5 M.f. C 14 H 18 N 4 O 4 S 2 Form Colourless crystalline solid. M.p. 195 °C (decomp.) Solubility Almost insoluble in water; sparingly soluble in most organic solvents. Stability Forms unstable solutions of salts with aqueous alkali and complexes with divalent transition metal ions, for example copper. COMMERCIALISATION: History Fungicide reported by K. Ishii (Abstr. Int. Congr. Plant Prot., 7th, Paris, 1970, p. 200); reviewed (idem, Jpn. Pestic. Inf., 1971, No. 7, p. 27). Introduced by Nippon Soda Co., Ltd. For thiophanate-methyl, see Main Entries. Patents DE 1930540 APPLICATIONS: Biochemistry Carbendazim (q.v.) precursor. Mode of action Systemic fungicide. Uses Effective against Venturia spp. on apple and pear crops, powdery mildews, Botrytis and sclerotinia spp. on various crops. Also used as an anthelminthic. Formulation types WP. PRODUCTS: Discontinued products ‘Cercobin’* (Nippon Soda); ‘Nemafax’* (anthelmintic) (May & Baker); ‘Topsin’* (Nippon Soda); ‘Verdamax’* (anthelmintic) (May & Baker). ANALYSIS: Product analysis by uv spectrometry. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986) is a general review of pesticides with a carbamate chemical structure. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male and female rats >15 000 mg/kg. Skin and eye Acute percutaneous LD 50 for male and female rats >15 000 mg/kg. Toxicity Class WHO (a.i.) U ENVIRONMENTAL FATE: Plants In plants it is converted into ethyl benzimidazol-2-ylcarbamate. thioquinox Acaricide, fungicide NOMENCLATURE: Common name thioquinox (BSI, E-ISO, (m) F-ISO, ESA) IUPAC name 1,3-dithiolo[4,5-b]quinoxaline-2-thione (I) Chemical Abstracts name (I) CAS RN [93–75–4] EC no 202–272–8 Development codes Bayer 30 686; Ss 1451 Smiles code S=c1sc2nc3ccccc3nc2s1 524 The Pesticide Manual Sixteenth Edition © BCPC 2012 tiocarbazil PHYSICAL CHEMISTRY: Mol. wt. 236.3 M.f. C 9 H 4 N 2 S 3 COMMERCIALISATION: History Acaricide and fungicide reported by G. Unterstenhöfer (Hoefchen-Briefe, (Engl. Ed.), 1960, 13, 207) and by K. Sasse (ibid., p. 197). Introduced by Bayer AG. PRODUCTS: Discontinued products ‘Eradex’* (Bayer); ‘Eraziton’* (Bayer). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22 tiocarbazil Herbicide HRAC N WSSA 8; thiocarbamate NOMENCLATURE: Common name tiocarbazil (BSI, E-ISO, (m) F-ISO) IUPAC name S-benzyl di-sec-butylthiocarbamate Chemical Abstracts name S-(phenylmethyl) bis(1-methylpropyl)carbamothioate CAS RN [36756–79–3] EC no 253–190–4 Development codes M 3432 (Agrimont) Smiles code CCC(C)N(C(C)CC)C(=O)SCc1ccccc1 PHYSICAL CHEMISTRY: Mol. wt. 279.4 M.f. C 16 H 25 NOS Form Colourless liquid, with aromatic odour. B.p. 130–132 °C /0.1 mmHg V.p. 93 mPa (50 °C) K ow logP = 4.4 S.g./density 1.023 (20 °C) Solubility In water 2.5 mg/l (30 °C). Miscible with polar and non-polar organic solvents. Stability Stable to hydrolysis at pH 5.6–8.4. Slightly decomposed after 30 days at 40 °C in aqueous ethanol at pH 1.5. Stable to storage for 60 days at 40 °C, and for 100 hours in aqueous solution exposed to sunlight. COMMERCIALISATION: History Herbicide reported by N. Caracalli et al. (Proc. Congr. Risicultura, 8th, 1973, p. 446). Introduced by Montedison S.p.A. (later Isagro S.p.A.) in Italy (1974). Patents IT 907710; DE 2144700 C N O S CH 3 CH 2 CH CH 3 CH 2 CH CH 2 CH 3 CH 3 Supplementary Entries – Extended tiocarbazil 525 APPLICATIONS: Biochemistry Inhibits lipid synthesis (not ACCase inhibition). Mode of action Selective herbicide, absorbed by the roots and coleoptiles. Uses Control of Echinochloa spp., Lolium perenne, Cyperus spp., and other monocotyledonous weeds in rice paddy felds. Applied pre- or post-emergence at 4 kg/ha, or as a seed dressing. Phytotoxicity Non-phytotoxic to rice. Formulation types EC; GR; SL; Seed treatment. PRODUCTS: Discontinued products ‘Drepamon’* (Isagro). ANALYSIS: Product and residue analysis by tlc (R. Fabbrini & G. Galluzzi, Anal. Methods Pestic. Plant Growth Regul., 1980, 11, 307). Product analysis also by glc method; details available from Isagro. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 76 (1988) is a general review of thiocarbamates. EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats, rabbits, and guinea pigs >10 000 mg tech./kg, for mice 8000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and rabbits >1200 mg/kg. Inhalation LC 50 for rats >0.18 mg/l air. NOEL In 2 y feeding trials, albino rats and beagle dogs receiving 1000 mg tech./kg diet suffered no ill-effect except for a slight weight loss in male dogs. No effect on reproduction in albino rats receiving 300 mg/kg diet for 3 generations. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Acute oral LD 50 for chickens, pheasants, quail >10 000 mg tech./kg. Fish LC 50 in several fsh species ≥8 mg/l. Other aquatic spp. LC 50 for the mollusc Australorbis glabratus >60 mg/l. Bees Not hazardous for honeybees. ENVIRONMENTAL FATE: Animals Tiocarbazil, when administered orally at the dose of 1 g/kg, is almost totally eliminated 7 days after treatment, either as such in the faeces or as products deriving from its metabolism, through the urine. In the blood and in the main organs, minimum concentrations of the product and of its metabolites have been found 48 hours after treatment. Plants Tiocarbazil undergoes extensive metabolism in rice: 3 compounds have been identifed in plants (except caryopsides): N,N-di-sec-butylcarbamoylthiolglycolic acid, N,N-di-sec-butylcarbamoyl benzylsulfoxide, and N,N-di-sec-butylcarbamoyl benzylsulfone (the frst by oxidation of the benzene ring, the other two by oxidation of the sulfur atom). Soil/Environment Tiocarbazil is strongly adsorbed by the soil (where it largely localises in the uppermost layer), Kom 1711, and undergoes a rapid degradation due to the attack of soil micro-organisms; 50% of tiocarbazil applied is no longer present in the soil/water system of a rice feld 8–15 days after treatment. 526 The Pesticide Manual Sixteenth Edition © BCPC 2012 tioxymid tioclorim Herbicide NOMENCLATURE: Common name tioclorime ((f) F-ISO); tioclorim (BSI, E-ISO) IUPAC name 6-chloro-5-(methylthio)pyrimidine-2,4-diamine Chemical Abstracts name 6-chloro-5-(methylthio)-2,4-pyrimidinediamine CAS RN [68925–41–7] Development codes UK-J 1506 (Produits Chimiques) Smiles code CSc1c(N)nc(N)nc1Cl PHYSICAL CHEMISTRY: Mol. wt. 190.6 M.f. C 5 H 7 ClN 4 S COMMERCIALISATION: History Herbicide discovered by Produits Chimiques Ugine Kuhlmann. tioxymid Fungicide NOMENCLATURE: Common name tioxymid (BSI, E-ISO); tioxymide ((m) F-ISO) IUPAC name 5-isothiocyanato-2-methoxy-N,N-dimethyl-m-toluamide Chemical Abstracts name 5-isothiocyanato-2-methoxy-N,N,3-trimethylbenzamide CAS RN [70751–94–9] Development codes SAF-787; 710 352-S Smiles code COc1c(C)cc(N=C=S)cc1C(=O)N(C)C PHYSICAL CHEMISTRY: Mol. wt. 250.3 M.f. C 12 H 14 N 2 O 2 S COMMERCIALISATION: History Fungicide introduced by Shionogi & Co., Ltd. Supplementary Entries – Extended N-m-tolylphthalamic acid 527 tolprocarb Fungicide NOMENCLATURE: Common name tolprocarb (pa ISO) IUPAC name 2,2,2-trifuoroethyl (S)-[2-methyl-1-(p-toluoylaminomethyl)propyl] carbamate Chemical Abstracts name 2,2,2-trifuoroethyl N-[(1S)-2-methyl-1-[[(4-methylbenzoyl) amino]methyl]propyl]carbamate CAS RN [911499–62–2] Development codes MTF– 0301 Smiles code Cc1ccc(cc1)C(=O)NC[C@H](C(C)C)/N=C(\O)/OCC(F)(F)F PHYSICAL CHEMISTRY: Mol. wt. 346.34 M.f. C 16 H 21 F 3 N 2 O 3 N-m-tolylphthalamic acid Plant growth regulator NOMENCLATURE: IUPAC name N-m-tolylphthalamic acid Other names N-m-t CAS RN [85–72–3] EC no 201–626–9 Smiles code Cc1cccc(NC(=O)c2ccccc2C(=O)O)c1 PHYSICAL CHEMISTRY: Mol. wt. 255.3 M.f. C 15 H 13 NO 3 Form White powder. M.p. 152 °C Solubility In water 0.1 g/l. COMMERCIALISATION: History Plant growth regulator. Manufacturers Makhteshim-Agan APPLICATIONS: Mode of action Systemic plant growth regulator which prevents abscission of fowers and young fruit. Uses Increases fruit set of tomatoes, aubergines and lima beans under CH 3 CH 3 CH 3 F F F NH N O OH O H CO 2 H CH 3 C NH O 528 The Pesticide Manual Sixteenth Edition © BCPC 2012 tralopyril adverse conditions. Formulation types WP. PRODUCTS: Discontinued products ‘Tomaset’* (Makhteshim-Agan). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved (as tolylphtalam), Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >20000 mg/kg. Inhalation LC 50 for rats >5 mg/l. tralopyril Anti-foulant, molluscicide See also The Manual of Biocontrol Agents entry: NOMENCLATURE: Common name tralopyril (BSI, E-ISO, (m) F-ISO) IUPAC name 4-bromo-2-(4-chlorophenyl)-5-(trifuoromethyl)-1H-pyrrole-3-carbonitrile Chemical Abstracts name 4-bromo-2-(4-chlorophenyl)-5-(trifuoromethyl)-1H- pyrrole-3-carbonitrile CAS RN [122454–29–9] Development codes AC 303268 Smiles code N#CC1=C(C2=CC=C(Cl)C=C2)NC(C(F)(F)F)=C1Br PHYSICAL CHEMISTRY: Mol. wt. 349.5 M.f. C 12 H 5 BrClF 3 N 2 N H N F F F Cl Br Supplementary Entries – Extended transpermethrin 529 transpermethrin Insecticide IRAC 3 An isomer pair, component of permethrin. NOMENCLATURE: Common name transpermé(thrine) ((f) F-ISO); transpermethrin (BSI, E-ISO) IUPAC name 3-phenoxybenzyl (1RS)-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropanecarboxylate; 3-phenoxybenzyl (1RS,3SR)-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate Chemical Abstracts name rel-(3-phenoxyphenyl)methyl (1R,3S)-3-(2,2- dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate; trans-(±)-(3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate Other names permethrin-G CAS RN [61949–77–7], formerly [52341–32–9]; [51877– 74–8] biopermethrin (the (1R)-trans- resolved isomer) (q.v.); [54774–47–9] (1S)-trans- isomer Development codes NRDC 146; RU 22090 Smiles code CC1(C)C(C=C(Cl)Cl)C1C(=O)OCc2cccc(Oc3ccccc3)c2 PHYSICAL CHEMISTRY: Mol. wt. 391.3 M.f. C 21 H 20 Cl 2 O 3 APPLICATIONS: Biochemistry Acts on the nervous system of insects, and disturbs the function of neurons by interaction with the sodium channel. O CH 2 C CH CH 3 CH 3 Cl C O O Cl O CH 2 C CH CH 3 CH 3 Cl C O O Cl H H H H (1R)-trans- isomer (biopermethrin) (1S)-trans- isomer 530 The Pesticide Manual Sixteenth Edition © BCPC 2012 triamiphos ANALYSIS: Analysis of pyrethroids reviewed by E. Papadopoulou-Mourkidou in Comp. Anal. Profles. Permethrin isomers in drinking water by glc with ECD (AOAC Methods, 18th Ed., 990.06). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: See A. J. Gray & D. M. Soderlund, Chapt. 5 in Insecticides. triamiphos Acaricide, fungicide, insecticide IRAC 1B NOMENCLATURE: Common name triamiphos (BSI, E-ISO, (m) F-ISO) IUPAC name 5-amino-3-phenyl-1H-1,2,4-triazol-1-yl-N,N,N′,N′-tetramethylphosphonic diamide Chemical Abstracts name P-(5-amino-3-phenyl-1H-1,2,4-triazol-1-yl)-N,N,N′,N′- tetramethylphosphonic diamide CAS RN [1031–47–6] Development codes WP 155 (Philips-Duphar) Smiles code CN(C)P(=O)(N(C)C)n1nc(nc1N)c2ccccc2 PHYSICAL CHEMISTRY: Composition Tech. is ≥95%. Mol. wt. 294.3 M.f. C 12 H 19 N 6 OP Form Colourless solid. M.p. 167–168 °C; (tech., 166–170 °C) Solubility In water 250 mg/l (20 °C). Moderately to easily soluble in most organic solvents. Stability Stable at room temperature under neutral or slightly alkaline conditions, but is readily hydrolysed by concentrated mineral acids. COMMERCIALISATION: History Acaricide, fungicide and insecticide reported by B. G. van den Bos et al. (Rec. Trav. Chim. Pays-Bas, 1960, 79, 807). Introduced by Philips-Duphar B.V. (later Uniroyal Chemical Co., Inc.). Patents NL 109510, US 3121090,US 3220922. APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic acaricide, fungicide and insecticide. Uses For powdery mildew control, at 25 g/100 l on apples and roses. Also has insecticidal and acaricidal properties. PRODUCTS: Discontinued products ‘Wepsyn 155’* (Philips-Duphar). ANALYSIS: Product and residue analysis is by the colorimetric determination of 5-phenyl-1,2,4-triazol- 3-ylamine formed on acid hydrolysis. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). Supplementary Entries – Extended triapenthenol 531 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 20 mg/kg. Toxicity Class WHO (a.i.) Ib EC Classifcation T+; R27/28 triapenthenol Plant growth regulator NOMENCLATURE: Common name triapenthé(nol) ((m) F-ISO); triapenthenol (BSI, E-ISO) IUPAC name (E)-(RS)-1-cyclohexyl-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical Abstracts name (E)-(±)-β-(cyclohexylmethylene)-α-(1,1-dimethylethyl)-1H- 1,2,4-triazole-1-ethanol CAS RN [76608–88–3] (E)- isomer Development codes BAY RSW 0411 Smiles code CC(C)(C)C(O)/C(=C/C1CCCCC1)/n2cncn2; without stereochemistry: CC(C)(C)C(O)C(=CC1CCCCC1)n2cncn2 PHYSICAL CHEMISTRY: Mol. wt. 263.4 M.f. C 15 H 25 N 3 O Form Colourless crystals. M.p. 135.5 °C V.p. 4.4 × 10 –3 mPa (20 °C) K ow logP = 2.274 Solubility In water 68 mg/l. In acetone 150, dichloromethane >200, hexane 5–10, methanol 433, isopropanol 100–200, toluene 20–50 (all in g/l). COMMERCIALISATION: History Plant growth regulator reported at 44th Deutsche Pfanzenschutz-Tag (1984), K. Lürssen & W. Reiser (Proc. 1985 Br. Crop Prot. Conf. - Weeds, 1, 121). Introduced in Belgium and France (1989) by Bayer AG. APPLICATIONS: Biochemistry The (S)-(-)- enantiomer is an inhibitor of gibberellin biosynthesis and a plant growth regulator; the (R)-(+)- enantiomer inhibits sterol demethylation and is fungicidal (K. Lürssen, Pfanz.-Nachr. Bayer (Eng. Ed.), 1988, 41, p. 306; U. Kraatz & L. Born, ibid., p. 340). Uses Plant growth regulator used to control lodging in oilseed rape and grasses grown for seed. (The (R)-(+)- enantiomer is fungicidal). Formulation types WG . PRODUCTS: Discontinued products ‘Baronet’* (Bayer). CH OH C N N N C(CH 3 ) 3 CH 532 The Pesticide Manual Sixteenth Edition © BCPC 2012 triarathene ANALYSIS: Residues determined by glc with TID (R. Brennecke, Pfanz.-Nachr. Bayer (Engl. Ed.), 1990, 43, 159). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000, micec. 4000, dogsc. 5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >5000 mg/kg. NOEL (2 y) for rats 100 mg/kg diet. Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Birds Acute oral LD 50 (14 d) for Japanese quail and hens >5000, for canaries (7 d) >1000 mg/kg. Fish LC 50 (96 h) for golden orfe 34.4, guppies 18.8, trout 37, and carp 18 mg/l. Daphnia LC 50 (48 h) >70 mg a.i. (as 70% WP)/l. Bees Not harmful to honeybees. triarathene Acaricide NOMENCLATURE: Common name triarathè(ne) ((m) F-ISO); triarathene (BSI, E-ISO, ANSI) IUPAC name 5-(4-chlorophenyl)-2,3-diphenylthiophene (I) Chemical Abstracts name (I) CAS RN [65691–00–1] Development codes UBI-T930 Smiles code Clc1ccc(cc1)c2cc(c(s2)c3ccccc3)c4ccccc4 PHYSICAL CHEMISTRY: Mol. wt. 346.9 M.f. C 22 H 15 ClS Form Colourless crystalline solid. M.p. 127 °C B.p. 462 °C V.p. 1.3 × 10 –6 mPa (25 °C) K ow logP = 8 Stability It is thermally stable at 127 °C; exposure to sunlight for several months causes a superfcial yellowing. COMMERCIALISATION: History Acaricide reported by D. I. Relyea et al. (Proc. Int. Congr. Plant Prot., 10th, 1983, 1, 355). Evaluated by Uniroyal Chemical Co., Inc. APPLICATIONS: Mode of action Contact acaricide. Uses Acaricide effective at 280–560 g/ha against eriophyoid mites (Aculus cornutus, Epitrimerus pyri and Phyllocoptruta oleivora) and at 2.26 kg/ha against Eutetranychus banksi, Panonychus ulmi and Tetranychus urticae. Its acaricidal action depends on the presence of daylight. The relationship between chemical structure and acaricidal activity has been discussed (D. I. Relyea et al., Proc. Int. Congr. Plant Prot., 10th, 1983, 1, 355). Formulation types WP. PRODUCTS: Discontinued products ‘Micromite’* (Uniroyal). Supplementary Entries – Extended triazbutil 533 MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >10 000 mg tech./kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Mild eye and no skin irritation (for the WP). Inhalation for rats >5.1 mg/l. ECOTOXICOLOGY: Birds LC 50 (8 d) for bobwhite quail and mallard duck >5620 mg/kg diet. Fish LC 50 (96 h) for bluegill and rainbow trout >100 mg/l. Daphnia LC 50 (48 h) 64 mg/l. triarimol Fungicide NOMENCLATURE: Common name triarimol (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name 2,4-dichloro-α-(pyrimidin-5-yl)benzhydryl alcohol Chemical Abstracts name α-(2,4-dichlorophenyl)-α-phenyl-5-pyrimidinemethanol CAS RN [26766–27–8] Development codes EL 273 Smiles code OC(c1ccccc1)(c2cncnc2)c3ccc(Cl)cc3Cl PHYSICAL CHEMISTRY: Mol. wt. 331.2 M.f. C 17 H 12 Cl 2 N 2 O COMMERCIALISATION: History Fungicide reported by J. V. Gramlich et al. (Proc. Br. Insectic. Fungic. Conf., 5th, 1969, 2, 576). Evaluated by Eli Lilly & Co. PRODUCTS: Discontinued products ‘Trimidal’* (Lilly). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O EC Classifcation Xn; R22 triazbutil Fungicide NOMENCLATURE: Common name triazbutil (BSI, E-ISO, (m) F-ISO, ANSI) IUPAC name 4-butyl-4H-1,2,4-triazole (I) Chemical Abstracts name (I) Other names butrizol CAS RN [16227–10–4] Development codes RH-124 Smiles code CCCCn1cnnc1 PHYSICAL CHEMISTRY: Mol. wt. 125.2 M.f. C 6 H 11 N 3 534 The Pesticide Manual Sixteenth Edition © BCPC 2012 tributyl phosphorotrithioite COMMERCIALISATION: History Fungicide evaluated by Rohm & Haas Co. PRODUCTS: Discontinued products ‘Indar’* (Rohm & Haas). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. tributyl phosphorotrithioite Plant growth regulator NOMENCLATURE: IUPAC name tributyl phosphorotrithioite (I) Chemical Abstracts name (I) Other names merphos CAS RN [150–50–5] Smiles code CCCCSP(SCCCC)SCCCC PHYSICAL CHEMISTRY: Composition Tech. is ≥95%. Mol. wt. 298.5 M.f. C 12 H 27 PS 3 Form Colourless to pale yellow liquid. B.p. 115–134 °C /0.08 mmHg S.g./density 0.99–1.01 (20 °C) Solubility Sparingly soluble in water; very soluble in most organic solvents. COMMERCIALISATION: History Introduced by the Mobil Chemical Co. and later by Rhône-Poulenc Agrochimie. Patents US 2955803 APPLICATIONS: Uses At 1.2–2.5 kg/ha to defoliate cotton. Can induce leaf abscission in some other plants, such as roses and hydrangeas. Formulation types AI. PRODUCTS: Discontinued products ‘Folex’* (Rhône-Poulenc Phytosanitaire). ANALYSIS: Product analysis by glc. Residues determined by glc with MCD. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male albino rats 1272 mg/kg. Skin and eye Acute percutaneous LD 50 for albino rabbits >4600 mg/kg. NOEL In 90 d feeding trials, dogs and rats receiving 750 mg/kg diet showed depression of cholinesterase but no other effect on pathology or histology. ADI/RfD (EPA) cRfD 0.00003 mg/kg b.w. [1991]. Supplementary Entries – Extended trichlamide 535 tricamba Herbicide NOMENCLATURE: Common name tricamba (BSI, E-ISO, (m) F-ISO, ANSI, WSSA) IUPAC name 3,5,6-trichloro-o-anisic acid Chemical Abstracts name 2,3,5-trichloro-6-methoxybenzoic acid CAS RN [2307–49–5] Smiles code COc1c(Cl)cc(Cl)c(Cl)c1C(=O)O PHYSICAL CHEMISTRY: Mol. wt. 255.5 M.f. C 8 H 5 Cl 3 O 3 COMMERCIALISATION: History Herbicide developed by Velsicol Corp. (later Sandoz AG). PRODUCTS: Discontinued products ‘Banvel T’* (Sandoz). MAMMALIAN TOXICOLOGY: Toxicity Class WHO (a.i.) O trichlamide Fungicide NOMENCLATURE: Common name trichlamide (BSI, E-ISO, (m) F-ISO) IUPAC name (RS)-N-(1-butoxy-2,2,2-trichloroethyl)salicylamide Chemical Abstracts name (±)-N-(1-butoxy-2,2,2-trichloroethyl)-2-hydroxybenzamide CAS RN [70193–21–4] Development codes NK-483 (Nippon Kayaku) Smiles code CCCCOC(NC(=O)c1ccccc1O)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 340.6 M.f. C 13 H 16 Cl 3 NO 3 Form Colourless crystals. M.p. 73–74 °C V.p. <10 mPa (20 °C) Solubility In water 6.5 mg/l. Soluble in acetone, alcohols, and benzene. Stability Stable ≤70 °C, and stable to light. COMMERCIALISATION: History Fungicide reported by T. Ohmori et al. (Plant Dis., 1986, 70, 51). Introduced in Japan (1985) by Nippon Kayaku Co., Ltd. Patents GB 2004540; DE 2837819; US 4200632 APPLICATIONS: Mode of action Non-systemic soil fungicide. Uses Control of diseases caused by Aphanomyces and Streptomyces spp., and related fungal diseases (e.g. club root, Root rots, scab, etc.) in potatoes and vegetables. Formulation types DP . PRODUCTS: Discontinued products ‘Hataclean’* (Nippon Kayaku). 536 The Pesticide Manual Sixteenth Edition © BCPC 2012 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate ANALYSIS: Product and residue analysis by glc. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats and mice >5000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats and mice >5000 mg/kg. Non-irritating to eyes and skin (rabbits). NOEL (2 y) for male rats 0.361 mg/kg, female rats 0.431 mg/kg daily. (2 y, gavage) for male dogs 10 mg/kg daily, for female dogs 2 mg/kg daily. Non-teratogenic in rats and rabbits. Other Acute i.p. LD 50 for male rats 1.54, female rats 1.14, male mice 1.59, female mice 1.66 mg/kg. Non-mutagenic in the Ames test, chromosomal aberration test, and micronucleus test (K. Fukunaga Jpn. Pestic. Inf. 1990, 56, 12–14). Toxicity Class WHO (a.i.) U ECOTOXICOLOGY: Fish LC 50 (48 h) for carp 1.7 mg/l. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 60–90 d. 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate Insecticide NOMENCLATURE: IUPAC name 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate Chemical Abstracts name 3,4-dichloro-α-(trichloromethyl)benzenemethyl acetate Other names benzethazet*; plifenate* (rejected common name proposals) CAS RN [21757–82–4] Development codes BAY MEB 6046 Smiles code CC(=O)OC(c1ccc(Cl)c(Cl)c1)C(Cl)(Cl)Cl PHYSICAL CHEMISTRY: Mol. wt. 336.4 M.f. C 10 H 7 Cl 5 O 2 Form Colourless crystalline solid. M.p. 84.5 °C V.p. 0.014 mPa (20 °C) Henry 9.42 × 10 –5 Pa m 3 mol –1 (calc.) Solubility In water 50 mg/ kg (20 °C). In cyclohexanone >600, isopropanol <10 (both in g/kg, 20 °C). COMMERCIALISATION: History Insecticide reported by W. Behrenz et al. (Pfanz.-Nachr. Bayer (Engl. Ed.), 1977, 30, 237). Introduced by Bayer AG. Patents DE 2110056 APPLICATIONS: Biochemistry The (-)- isomer is more active. Mode of action Contact insecticide with respiratory action and long residual activity. Uses It was recommended for use against such pests as clothes moths, fies and mosquitoes. Formulation types AE; DP; UL . PRODUCTS: Discontinued products ‘Baygon MEB’* (Bayer); ‘Penfenate’* (Bayer). Supplementary Entries – Extended trichlorobenzyl chloride 537 ANALYSIS: Product and residue analysis by glc with ECD. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >10 000 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg. Inhalation (4 h) for rats >0.7 mg/l air. NOEL (90 d) for rats 1000 mg/kg diet. ECOTOXICOLOGY: Birds Acute oral LD 50 for hens >2500 mg/kg. Fish LC 50 (96 h) for orfe 0.5–1.0 mg/l. ENVIRONMENTAL FATE: Animals Following oral adminstration, there is no concentration in adipose tissue or liver, kidney or brain. The alcohol has been isolated as a metabolite in animal tissue (W. Behrenz et al., Pfanz.-Nachr. Bayer 1977, 30, 237). 4,5,7-trichloro-2,1,3-benzothiadiazole Herbicide NOMENCLATURE: IUPAC name 4,5,7-trichloro-2,1,3-benzothiadiazole (I) Chemical Abstracts name (I) CAS RN [1982–55–4] Development codes PH 40–21 Smiles code Clc1cc(Cl)c2nsnc2c1Cl PHYSICAL CHEMISTRY: Mol. wt. 239.5 M.f. C 6 HCl 3 N 2 S COMMERCIALISATION: History Herbicide reported by J. Dams et al. (Proc. Br. Weed Control Conf., 7th, 1964, p. 1091). Evaluated by Philips-Duphar B.V. (later Uniroyal Chemical Co., Inc.). trichlorobenzyl chloride Herbicide NOMENCLATURE: IUPAC name trichlorobenzyl chloride Chemical Abstracts name trichloro(chloromethyl)benzene Other names TCBC CAS RN [1344–32–7], formerly [25429–36–1] Smiles code ClCc1c(Cl)ccc(Cl)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 229.9 M.f. C 7 H 4 Cl 4 COMMERCIALISATION: History Herbicide introduced by Monsanto Co. 538 The Pesticide Manual Sixteenth Edition © BCPC 2012 trichloronat PRODUCTS: Discontinued mixtures ‘Randox-T’* (+ allidochlor) (Monsanto). trichloronat Insecticide IRAC 1B NOMENCLATURE: Common name trichloronate (BSI (before 1984), France); trichloronat (BSI (since 1984), E-ISO, (m) F-ISO) IUPAC name O-ethyl O-2,4,5-trichlorophenyl ethylphosphonothioate Chemical Abstracts name O-ethyl O-(2,4,5-trichlorophenyl) ethylphosphonothioate CAS RN [327–98–0] EC no 206–326–1 Development codes Bayer 37 289; S 4400 Smiles code CCOP(=S)(CC)Oc1cc(Cl)c(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 333.6 M.f. C 10 H 12 Cl 3 O 2 PS Form Amber-coloured liquid. B.p. 108 °C /0.01 mmHg V.p. 2 mPa (20 °C) Henry 1.33 × 10-2 Pa m 3 mol –1 (calc.) S.g./density 1.365 (20 °C) Solubility In water 50 mg/l (20 °C). In dichloromethane, isopropanol >1.2 kg/kg (20 °C). Stability Hydrolysed by alkali. COMMERCIALISATION: History Insecticide reported by R. O. Drummond (J. Econ. Entomol., 1963, 56, 831). Introduced by Bayer AG. Patents DE 1099530 APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide. Uses It was recommended for the control of root maggots, other soil-dwelling insects and wireworms. Formulation types EC; GR; Seed treatment. PRODUCTS: Discontinued products ‘Agrisil’* (Bayer); ‘Agritox’* (Bayer); ‘Phytosol’* (Bayer). ANALYSIS: Product analysis by uv spectroscopy after hydrolysis to 2,4,5-trichlorophenol. Residues determined by glc (E. Mõllhoff, Pfanz.-Nachr. Bayer (Engl. Ed.), 1968, 21, 331). See also Pestic. Anal. Man., I, 302. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Evaln. 17 (1971). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 16–37.5, rabbits 25–50 mg/kg. Skin and eye Acute percutaneous LD 50 for male rats 135–341 mg/kg. NOEL In 2 y feeding trials, rats receiving 3 mg/kg diet showed no symptom of poisoning. ADI/RfD (JMPR) No ADI [1971]. Toxicity Class WHO (a.i.) Ia EC Classifcation T+; R28| T; R24| N; R50, R53 Supplementary Entries – Extended tridiphane 539 triclopyricarb Fungicide NOMENCLATURE: Common name triclopyricarb (pa ISO) IUPAC name methyl N-methoxy-2-(3,5,6-trichloro-2-pyridyloxymethyl)carbanilate Chemical Abstracts name methyl N-methoxy-N-[2-[[(3,5,6-trichloropyridin-2-yl)oxy] methyl]phenyl]carbamate CAS RN [902760–40–1] Development codes SYP–7017 Smiles code COC(=O)N(c1ccccc1COc2c(cc(c(n2)Cl)Cl)Cl)OC PHYSICAL CHEMISTRY: Mol. wt. 391.63 M.f. C 15 H 13 Cl 3 N 2 O 4 tridiphane Herbicide NOMENCLATURE: Common name tridiphane (BSI, ANSI, E-ISO) IUPAC name (RS)-2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethyl)oxirane Chemical Abstracts name (±)-2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethyl)oxirane CAS RN [58138–08–2] Development codes Dowco 356 Smiles code Clc1cc(Cl)cc(c1)C2(CC(Cl)(Cl)Cl)CO 2 PHYSICAL CHEMISTRY: Mol. wt. 320.4 M.f. C 10 H 7 Cl 5 O Form Colourless crystals. M.p. 42.8 °C V.p. 29 mPa (25 °C) K ow logP = 4.34 Henry 5.16 Pa m 3 mol –1 (calc.) Solubility In water 1.8 mg/l (25 °C). In methanol 0.98, acetone 9.1, xylene 4.6, chlorobenzene 5.6, dichloromethane 7.1 (all in kg/kg, 25 °C). Stability Hydrolysis DT 50 80 d (pH 5–9, 35 °C) (ARS PPD). F.p. 46.7 °C COMMERCIALISATION: History Herbicide reported by E. S. Saunders et al. (Proc. North Cent. Weed Control Conf., 1981, p. 133). Introduced by Dow Chemical Co. (later DowElanco). Patents US 4211549; EP 81351 CH OH C N N N C(CH 3 ) 3 CH 540 The Pesticide Manual Sixteenth Edition © BCPC 2012 trifenmorph APPLICATIONS: Mode of action Selective non-systemic herbicide, absorbed by the leaves and roots. Uses Control of annual grass seedlings and broad-leaved weeds in maize. Applied post- emergence in combination with triazine herbicides. Formulation types EC. PRODUCTS: Discontinued products ‘Nelpon’* (DowElanco); ‘Tandem’* (DowElanco). ANALYSIS: Product analysis by hplc. Residues determined by glc/ECD (Pestic. Anal. Man., II, 180.424; Resid. Anal. Methods). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 1743–1918 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits 3536 mg/kg. Moderately irritating to eyes and skin (rabbits). Potential skin sensitiser. NOEL (2 y) for rats 3 mg/kg daily. ADI/RfD (EPA) cRfD 0.003 mg/kg b.w. [1992]. Toxicity Class WHO (a.i.) III ECOTOXICOLOGY: Birds Acute oral LD 50 for mallard ducks >2510 mg/kg. Dietary LC 50 (8 d) for mallard ducks and bobwhite quail 5620 mg/kg diet. Fish LC 50 (96 h) for rainbow trout 0.53, bluegill sunfsh 0.37 mg/l. ENVIRONMENTAL FATE: Soil/Environment Soil DT 50 (ave.) 26 d, under aerobic conditions. trifenmorph Molluscicide NOMENCLATURE: Common name trifenmorph (BSI, E-ISO); triphenmorphe ((m) F-ISO) IUPAC name 4-tritylmorpholine Chemical Abstracts name 4-(triphenylmethyl)morpholine CAS RN [1420–06–0] EC no 215–812–2 Development codes WL 8008 (Shell) Smiles code C1CN(CCO1)C(c2ccccc2)(c3ccccc3)c4ccccc4 PHYSICAL CHEMISTRY: Composition Tech. is 90–95%. Mol. wt. 329.4 M.f. C 23 H 23 NO Form Colourless crystalline solid. M.p. 176–178 °C, resolidifying and remelting at 185–187 °C; (tech. melts 150–170 °C, and again at 170–185 °C) V.p. 1.9 × 10-2 mPa (20 °C) Henry 3.13 × 10 –1 Pa m 3 mol –1 (calc.) Solubility In water 0.02 mg/l (20 °C). In carbon tetrachloride 300, chloroform 450, tetrachloroethylene 255 (all in g/l, 20 °C). Stability Stable to heat and alkali, but hydrolysed by mild acid to morpholine and triphenylmethanol. Slight decomposition occurs in uv light. Supplementary Entries – Extended trifenofos 541 COMMERCIALISATION: History Molluscicide reported by C. B. C. Boyce et al. (Nature (London), 1966, 210, 1140). Introduced by Shell Research Ltd. APPLICATIONS: Uses Effective against aquatic and semi-aquatic snails. Recommended for application to irrigation and other moving water systems, at 0.03–0.01 mg/l, and in static water atc. 1.0–2.0 mg/l. Also recommmended for application to Lymnaea truncatula habitats, at 500 g/ha, to control fascioliasis. PRODUCTS: Discontinued products ‘Frescon’* (Shell). ANALYSIS: Product analysis is by non-aqueous titration with a perchloric-acetic acid mixture (Pesticides used in Public Health, p. 248) or by hplc. Residues may be determined colorimetrically with cyclohaxane-sulfuric acid (K. I. Beynon & G. R. Thomas, Bull, WHO, 1967, 37, 47); a method suitable for use under feld conditions is available (K. I. Beynon & A. N. Wright, Pestic. Sci., 1975, 6, 515). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: PDS 64 (1985). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 446–2200, mice 700–4800 mg/kg. Toxicity Class WHO (a.i.) III EC Classifcation Xn; R22| N; R50, R53 ENVIRONMENTAL FATE: Plants In plants, and in soil and water, broken down initially to triphenylmethanol (K. I. Beynon, et al., Pestic. Sci., 1972, 3, 689). Soil/Environment See plants. trifenofos Acaricide, insecticide IRAC 1B NOMENCLATURE: Common name trifenofos (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name O-ethyl S-propyl O-2,4,6-trichlorophenyl phosphorothioate Chemical Abstracts name O-ethyl S-propyl O-(2,4,6-trichlorophenyl) phosphorothioate CAS RN [38524–82–2] Development codes RH-218; RH-8218 Smiles code CCCSP(=O)(OCC)Oc1c(Cl)cc(Cl)cc1Cl PHYSICAL CHEMISTRY: Mol. wt. 363.6 M.f. C 11 H 14 Cl 3 O 3 PS COMMERCIALISATION: History Acaricide and insecticide introduced by Rohm & Haas Co. 542 The Pesticide Manual Sixteenth Edition © BCPC 2012 trifopsime APPLICATIONS: Biochemistry Cholinesterase inhibitor. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). trifop; trifop-methyl Herbicide NOMENCLATURE: Common name trifop (BSI, E-ISO, (m) F-ISO) IUPAC name (RS)-2-[4-(α,α,α-trifuoro-p-tolyloxy)phenoxy]propionic acid Chemical Abstracts name (±)-2-[4-[4-(trifuoromethyl)phenoxy]phenoxy]propanoic acid CAS RN [58594–74–4] trifop (unstated stereochemistry); [59011–30–2] trifop (racemate); [58594–77–7] trifop-methyl (unstated stereochemistry); [59011–33–5] trifop- methyl (racemate) Development codes Hoe 29 152 (trifop-methyl) PHYSICAL CHEMISTRY: Mol. wt. 326.3; (methyl ester 340.3) M.f. C 16 H 13 F 3 O 4 ; (methyl ester C17H15F3O4) COMMERCIALISATION: History Herbicide evaluated by Hoechst AG. trifopsime Herbicide NOMENCLATURE: Common name trifopsime (BSI, E-ISO, (f) F-ISO) IUPAC name acetone (R)-O-[2-[4-(α,α,α-trifuoro-p-tolyloxy)phenoxy]propionyl]oxime Chemical Abstracts name (R)-2-propanone O-[1-oxo-2-[4-[4-(trifuoromethyl) phenoxy]phenoxy]propyl]oxime CAS RN [72131–76–1] Development codes Ro 13–8895 Smiles code CC(Oc1ccc(Oc2ccc(cc2)C(F)(F)F)cc1)C(=O)ON=C(C)C PHYSICAL CHEMISTRY: Mol. wt. 381.4 M.f. C 19 H 18 F 3 NO 4 COMMERCIALISATION: History Herbicide evaluated by Hofmann-La Roche Ltd. Supplementary Entries – Extended trimethacarb 543 trimethacarb Insecticide, molluscicide IRAC 1A; carbamate NOMENCLATURE: Common name trimethacarb (BSI, ANSI, E-ISO) IUPAC name Reaction product comprising 3,4,5-trimethylphenyl methylcarbamate (I) and 2,3,5-trimethylphenyl methylcarbamate (II) in a ratio between 3.5:1 and 5.0:1 m/m Chemical Abstracts name 2,3,5(or 3,4,5)-trimethylphenyl methylcarbamate CAS RN [12407–86–2] trimethacarb; [2686–99–9] (I); [2655–15–4] (II) Development codes UC 27 867 (Union Carbide); SD 8530 (Shell) Offcial codes OMS 597 Smiles code 2,3,5-isomer:CNC(=O)Oc1cc(C)cc(C)c1C;3,4,5-isomer:CNC(=O) Oc1cc(C)c(C)c(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 193.2 M.f. C 11 H 15 NO 2 Form Buff to brown, crystalline solid. M.p. 105–114 °C V.p. 6.8 mPa (25 °C) Henry 2.27 × 10-2 Pa m 3 mol –1 (calc.) Solubility In water >58 mg/ kg (23 °C). Not readily soluble in organic solvents. Stability Decomposed by strong acids and alkalis. Stable to light. COMMERCIALISATION: History Insecticide originally introduced by Shell Development Co. (now E. I. du Pont de Nemours & Co.) and later by Union Carbide Agrochemicals (now Bayer AG, who no longer manufacture or market it). APPLICATIONS: Biochemistry Cholinesterase inhibitor Mode of action Insecticide with predominantly stomach action, but also some contact action. Long residual activity. Uses Control of corn rootworms larvae in maize. Also controls a wide range of insect and mollusc pests, and acts as a mammal and bird repellent. Phytotoxicity Non-phytotoxic when used as directed. Phytotoxic to the seeds of some crops, including maize, sorghum, wheat and rice. Formulation types GR; WP. PRODUCTS: Discontinued products ‘Broot’* (Drexel); ‘Landrin’* (Shell). CH 3 CH 3 OCONHCH 3 CH 3 CH 3 CH 3 OCONHCH 3 CH 3 3,4,5- isomer 2,3,5- isomer 544 The Pesticide Manual Sixteenth Edition © BCPC 2012 triprene ANALYSIS: Residues by glc with ECD (S. C. Lau & R. L. Marxmiller, J. Agric. Food Chem., 1970, 18, 413–415). See also Pestic. Anal. Man., II, 180.305. In soil by gc/NPD (Environ. Chem. Methods). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 130 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. NOEL (2 y) for rats 50 ppm (2.5 mg/kg b.w.) (EPA Tracking). ADI/RfD (EPA) 0.0025 mg/kg b.w. [1986]. Toxicity Class WHO (a.i.) O. ECOTOXICOLOGY: Fish Toxic to fsh. Bees Toxic to bees, in spray formulations. ENVIRONMENTAL FATE: Animals Metabolism of carbamate insecticides is reviewed (M. Cool & C. K. Jankowski in Insecticides). Plants In plants, metabolism occurs via hydroxylation of the N-methyl group and at the 3- and 4-methyl positions. All metabolites may be conjugated as glucosides. Soil/Environment Soil DT 50 c. 60 d in sterile soil. trimeturon Herbicide NOMENCLATURE: Common name trimeturon (BSI, (m) France) IUPAC name 3-(4-chlorophenyl)-1,1,2-trimethylisourea Chemical Abstracts name methyl N′-(4-chlorophenyl)-N,N- dimethylcarbamimidate CAS RN [3050–27–9] Development codes BAY 40 557 Smiles code COC(=Nc1ccc(Cl)cc1)N(C)C PHYSICAL CHEMISTRY: Mol. wt. 212.7 M.f. C 10 H 13 ClN 2 O COMMERCIALISATION: History Herbicide evaluated by Bayer AG. triprene Insecticide NOMENCLATURE: Common name triprene (BSI, E-ISO, (m) F-ISO, ANSI, ESA) IUPAC name S-ethyl (E,E)-(RS)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienethioate Supplementary Entries – Extended tritac 545 Chemical Abstracts name (2E,4E)-S-ethyl 11-methoxy-3,7,11-trimethyl- 2,4-dodecadienethioate CAS RN [40596–80–3], formerly [53023–54–4] Development codes ZR 619 Smiles code CCSC(=O)C=C(C)C=CCC(C)CCCC(C)(C)OC PHYSICAL CHEMISTRY: Mol. wt. 312.5 M.f. C 18 H 32 O 2 S COMMERCIALISATION: History Insect growth regulator introduced by Zoecon Corp. (later Sandoz AG). APPLICATIONS: Mode of action Insect growth regulator. PRODUCTS: Discontinued products ‘Altorick’* (Sandoz). tripropindan Herbicide NOMENCLATURE: Common name tripropindan (BSI, E-ISO); tripropindane ((m) F-ISO) IUPAC name 1-(6-isopropyl-1,1,4-trimethylindan-5-yl)propan-1-one Chemical Abstracts name 1-[2,3-dihydro-1,1,4-trimethyl-6-(1-methylethyl)-1H- inden-5-yl]-1-propanone CAS RN [6682–77–5] Development codes Ro 7–0668 Smiles code CC(C)c1cc2c(CCC2(C)C)c(C)c1CC(=O)C PHYSICAL CHEMISTRY: Mol. wt. 258.4 M.f. C 18 H 26 O COMMERCIALISATION: History Herbicide evaluated by Roche. tritac Herbicide NOMENCLATURE: Common name tritac (WSSA) IUPAC name 1-(2,3,6-trichlorobenzyloxy)propan-2-ol Chemical Abstracts name 1-[(2,3,6-trichlorophenyl)methoxy]-2-propanol CAS RN [1861–44–5] Smiles code CC(O)COCc1c(Cl)ccc(Cl)c1Cl PHYSICAL CHEMISTRY: Mol. wt. 269.6 M.f. C 10 H 11 Cl 3 O 2 546 The Pesticide Manual Sixteenth Edition © BCPC 2012 urbacid COMMERCIALISATION: History Herbicide introduced by Hooker Chemical Corp. PRODUCTS: Discontinued products ‘Tritac’* (Hooker). UBI-S734 Herbicide NOMENCLATURE: IUPAC name 2-pyridyl 1-(2,5-xylyl)ethyl sulfone 1-oxide Chemical Abstracts name 2-[[1-(2,5-dimethylphenyl)ethyl]sulfonyl]pyridine 1-oxide CAS RN [60263–88–9] Development codes UBI-S734 Smiles code CC(c1cc(C)ccc1C)S(=O)(=O)c2cccc[n+]2[O-] PHYSICAL CHEMISTRY: Mol. wt. 291.4 M.f. C 15 H 17 NO 3 S COMMERCIALISATION: History Herbicide evaluated by Uniroyal Chemical Co., Inc. urbacid Fungicide NOMENCLATURE: Common name urbacid (JMAF) IUPAC name methylarsinediyl bis(dimethyldithiocarbamate) Chemical Abstracts name dimethylcarbamodithioic acid bis(anhydrosulfde) with methylarsonodithious acid CAS RN [2445–07–0] Smiles code CN(C)C(=S)S[As](C)SC(=S)N(C)C PHYSICAL CHEMISTRY: Mol. wt. 330.4 M.f. C 7 H 15 AsN 2 S 4 Form Colourless crystals. M.p. 144 °C V.p. Low volatility Solubility Insoluble in water. Soluble in most organic solvents. COMMERCIALISATION: History Fungicide introduced by Bayer AG. Patents US 2644005; DE 833271 APPLICATIONS: Mode of action Protective fungicide. Uses Sprays were used at 240–480 g a.i. (as 800 g/ kg WP)/ha. It showed promise against Venturia inaequalis on apples, and was mainly used as a mixture with thiram and ziram. Formulation types WP. Supplementary Entries – Extended vamidothion 547 PRODUCTS: Discontinued products ‘Monzet’* (Bayer); ‘Urbacid’* (Bayer); Discontinued mixtures ‘Tuzet’* (+ thiram + ziram) (Bayer). ANALYSIS: Product analysis was by a titrimetric method. Residues may be determined by a colorimetric method after conversion to arsenate (H. Frehse & H.Tietz, J. Agric. Food Chem., 1959, 7, 553). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: Arsenic and arsenic compounds are reviewed in EHC 224 (2001). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 175 mg/kg. EC Classifcation Not specifed, but arsenic compounds in general (with exceptions) are assigned T; R23/25| N; R50, R53 (concentration-dependent) vamidothion Acaricide, insecticide IRAC 1B; organophosphate NOMENCLATURE: Common name vamidothion (BSI, E-ISO, (m) F-ISO, JMAF) IUPAC name O,O-dimethyl S-2-(1-methylcarbamoylethylthio)ethyl phosphorothioate; 2-(2-dimethoxyphosphinoylthioethylthio)-N-methylpropionamide Chemical Abstracts name O,O-dimethyl S-[2-[[1-methyl-2-(methylamino)-2- oxoethyl]thio]ethyl] phosphorothioate CAS RN [2275–23–2] EC no 218–894–8 Development codes 10 465 RP (Rhône-Poulenc); NPH 83 Offcial codes ENT 26 613 Smiles code CNC(=O)C(C)SCCSP(=O)(OC)OC PHYSICAL CHEMISTRY: Mol. wt. 287.3 M.f. C 8 H 18 NO 4 PS 2 Form Colourless needles; (tech., white, waxy solid). M.p. c. 43 °C; (tech., 40 °C) V.p. Negligible (20 °C) Solubility Readily soluble in water (4 kg/l), benzene, toluene, methyl ethyl ketone, ethyl acetate, acetonitrile, dichloromethane, cyclohexanone, chloroform (allc. 1 kg/l). Almost insoluble in cyclohexane and petroleum ether. Stability Undergoes slight decomposition at room temperature, but solutions in organic solvents (methyl ethyl ketone, cyclohexanone) are stable. Decomposed in strong acidic or alkaline media. S P(OCH 3 ) 2 O CH 2 CH 2 S CH C CH 3 CH 3 NH O 548 The Pesticide Manual Sixteenth Edition © BCPC 2012 vamidothion COMMERCIALISATION: History Insecticide reported by J. Desmoras et al. (Phytiatr.-Phytopharm., 1962, 11, 107). Introduced by Rhône-Poulenc Agrochimie (later Bayer AG). Patents GB 872823; BE 575106 Manufacturers Bayer CropScience APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Systemic insecticide and acaricide. Metabolised in plants to the corresponding sulfoxide, which is of similar activity to vamidothion but of greater persistence. Uses Systemic insecticide giving persistent control of Eriosoma lanigerum and other piercing and sucking Homoptera in cotton, hops, pome and stone fruit, and rice, at 37–50 g/hl. Formulation types EC. PRODUCTS: Discontinued products ‘Asystin Z’* (Kwizda); ‘Kilval’* (Bayer CropScience); ‘Kilvar’* (Japan) (Bayer CropScience); ‘Trucidor’* (Rhône-Poulenc); ‘Vamidoate’* (Rhône-Poulenc). ANALYSIS: Product analysis by hplc or glc (J. Desmoras et al., Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 479). Residues determined by glc (idem, ibid.; Man. Pestic. Residue Anal., pp. 3, 6, 13; Anal. Methods Residues Pestic., 1988, Part I, M2, M5, M10; A. Ambrus et al., J. Assoc. Off. Anal. Chem., 1981, 64, 733; A. R. C. Hill, Analyst (London), 1984, 109, 483). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 63 (1986; a general review of organophosphorus insecticides). JMPR Mtg. 65 (1992); JMPR Evaln. I 66 (1992); JMPR Evaln. II 55 (1988). ICSC.758 (2001). EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 100–105, female rats 64–67, mice 34–37 mg/kg. For the sulfoxide, acute oral LD 50 for male rats 160, mice 80 mg/kg. Skin and eye Acute percutaneous LD 50 for mice 1460, rabbits 1160 mg/kg. Inhalation LC 50 (4 h) for rats 1.73 mg/l air. NOEL In 90 d feeding trials, the growth rate of rats receiving 50 mg vamidothion/kg diet or 100 mg of its sulfoxide/kg diet was unaffected. ADI/RfD (JMPR) 0.008 mg/kg b.w. [1988]. Toxicity Class WHO (a.i.) Ib EC Classifcation T; R25| Xn; R21| N; R50 ECOTOXICOLOGY: Birds Acute oral LD 50 for pheasants 35 mg/kg. Fish LC 50 (96 h) for zebra fsh 590 mg/l. At 10 mg/l, harmless to goldfsh (14 d). Daphnia EC 50 (48 h) 0.19 mg/l. Bees Toxic to bees. ENVIRONMENTAL FATE: Animals Oxidised to the sulfoxide and sulfone, followed by cleavage of the P-S and S-C bonds, to give water-soluble metabolites. Plants Metabolised in plants to the corresponding sulfoxide, which appears within hours after treatment. Also demethylation and hydrolysis to phosphoric acid. After 20 days, all the toxic residues in the plant are in the form of the sulfoxide. Soil/Environment In soil, DT 50 1.0–1.5 d (aerobic, 22 °C). Supplementary Entries – Extended vernolate 549 vaniliprole Acaricide, insecticide NOMENCLATURE: Common name vaniliprole (BSI, E-ISO, (m) F-ISO, not Denmark) IUPAC name (E)-1-(2,6-dichloro-α,α,α-trifuoro-p-tolyl)-5-(4-hydroxy-3- methoxybenzylidenamino)-4-trifuoromethylthiopyrazole-3-carbonitrile Chemical Abstracts name 1-[2,6-dichloro-4-(trifuoromethyl)phenyl]-5-[[(E)-(4- hydroxy-3-methoxyphenyl)methylene]amino]-4-[(trifuoromethyl)thio]-1H-pyrazole- 3-carbonitrile CAS RN [145767–97–1] Development codes RPA-098231 (Rhône- Poulenc) PHYSICAL CHEMISTRY: Mol. wt. 555.3 M.f. C 20 H 10 Cl 2 F 6 N 4 O 2 S COMMERCIALISATION: Manufacturers Rhône-Poulenc APPLICATIONS: Uses Foliar insecticide and acaricide for use in cotton, vines, vegetables etc. PRODUCTS: Discontinued products ‘Evaluation’* (Aventis). vernolate Herbicide HRAC N WSSA 8; thiocarbamate NOMENCLATURE: Common name vernolate (BSI, E-ISO, (m) F-ISO, WSSA, JMAF) IUPAC name S-propyl dipropylthiocarbamate Chemical Abstracts name S-propyl dipropylcarbamothioate CAS RN [1929–77–7] N N CN CF 3 S N C CF 3 Cl Cl CH 3 O HO H C N O S CH 3 (CH 2 ) 2 CH 3 (CH 2 ) 2 CH 2 CH 2 CH 3 550 The Pesticide Manual Sixteenth Edition © BCPC 2012 vernolate EC no 217–681–7 Development codes R-1607 (Stauffer) Smiles code CCCSC(=O)N(CCC)CCC PHYSICAL CHEMISTRY: Composition Tech. material is 95% pure. Mol. wt. 203.3 M.f. C 10 H 21 NOS Form Clear liquid, with slight aromatic odour; (tech. is a clear yellow liquid). B.p. 150 °C /30 mmHg V.p. 1.39 Pa (25 °C) K ow logP = 3.84 (20 °C) S.g./density 0.952 g/ml (20 °C) Solubility In water 90 mg/l (20 °C). Miscible with common organic solvents, e.g. xylene, methyl isobutyl ketone, kerosene, acetone, ethanol. Stability Stable in neutral media, and relatively stable in acidic and alkaline media; DT 50 13 d (pH 7, 40 °C). Stable up to 200 °C. Decomposed by sunlight. F.p. 121 °C COMMERCIALISATION: History Herbicide introduced by Stauffer Chemical Co. (became Zeneca Agrochemicals). First registered in USA in 1964. Patents US 2913327 APPLICATIONS: Biochemistry Inhibits lipid synthesis (not ACCase inhibition). Mode of action Selective herbicide, absorbed by the roots, with translocation to the stems and leaves. Germination inhibitor. Uses Control of germinating broad-leaved and grass weeds in peanuts, soya beans, maize, tobacco and sweet potatoes, at 1.5–3.0 kg/ha. Soil incorporation is necessary, either pre-planting or pre-emergence. Formulation types EC; GR . PRODUCTS: Discontinued products ‘Reward’* (Zeneca); ‘Saverit’* (Chemolimpex); ‘Savirox’* (Chemolimpex); ‘Vernam’* (Drexel). ANALYSIS: Product analysis by glc with FID (AOAC Methods, 18th Ed., 974.05; CIPAC Handbook, 1983, 1B, 1905); see also method for butylate, (ibid., 1983, 1B, 1744). Residues in crops and soils determined by glc or by colorimetry after conversion to a derivative (G. G. Patchett & G. H. Batchelder, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1967, 5, 337; W. J. Ja, Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 708). See also Pestic. Anal. Man., II, 180.240. In soil, also by gc/NPD (Environ. Chem. Methods). In drinking water by glc with NPD (AOAC Methods, 18th Ed., 991.07). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EU Status (1107/2009) Not approved, Commission Regulation 2076/2002. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 1500, female rats 1550 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >5000 mg/kg. Non-irritating to eyes and skin (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC 50 (4 h) for rats >5 mg/l. NOEL NOAEL (2 generation) for rats 1 mg/kg b.w. (EPA RED); NOEL (90 d) for rats 32 mg/kg, for dogs 38 mg/kg daily. ADI/RfD (EPA) cRfD 0.001 mg/kg b.w. [1992, 1999, 2004]. Toxicity Class WHO (a.i.) II EPA (formulation) III EC Classifcation Xn; R22| N; R51, R53 Supplementary Entries – Extended WL 9385 551 ECOTOXICOLOGY: Birds Dietary LC 50 (7 d) for bobwhite quail 12 000 mg/kg. Fish LC 50 (96 h) for rainbow trout 4.6, bluegill sunfsh 8.4 mg/l. Bees Non-toxic to bees at 0.011 mg/bee. ENVIRONMENTAL FATE: Plants Readily metabolised by plants to CO 2 and naturally-occurring plant constituents. Soil/Environment In soil, microbial decomposition to mercaptan, amine, isopropanol and CO 2 . DT 50 (27 °C) 8–16 d; (4 °C) >64 d. WL 108 477 Insecticide IRAC 4A NOMENCLATURE: IUPAC name 2-nitromethylene-1,3-thiazinan-3-ylcarbamaldehyde Chemical Abstracts name dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)- carboxaldehyde CAS RN [94050–50–7] Development codes WL 108 477 PHYSICAL CHEMISTRY: Mol. wt. 188.2 M.f. C 6 H 8 N 2 O 3 S Form Pale yellow crystals. M.p. 138–140 °C (decomp.). K ow logP = 0.23 Solubility In water 500 mg/l (20 °C). In xylene 2.5 g/l. COMMERCIALISATION: History Insecticide reported by M. Harris et al. (Proc. 1986 Brit. Crop Prot. Conf. - Pests Dis., 1, 115). Introduced by Shell Research Limited (became American Cyanamid Co.). Manufacturers Cyanamid APPLICATIONS: Biochemistry Neurotoxic insecticide. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for mice 1000–2500 mg/kg. Skin and eye Acute percutaneous LD 50 for mice >600 mg/kg. ECOTOXICOLOGY: Fish LD 50 (96 h) for rainbow trout >100 mg/l. WL 9385 Herbicide NOMENCLATURE: IUPAC name 2-azido-4-tert-butylamino-6-ethylamino-1,3,5-triazine; 6-azido-N 2 -tert- butyl-N4-ethyl-1,3,5-triazine-2,4-diamine 552 The Pesticide Manual Sixteenth Edition © BCPC 2012 XMC Chemical Abstracts name 6-azido-N-(1,1-dimethylethyl)-N′-ethyl-1,3,5- triazine-2,4-diamine CAS RN [2854–70–8] Development codes WL 9385 Smiles code CCNc1nc(NC(C)(C)C)nc([N-][N+]#N)n1 PHYSICAL CHEMISTRY: Mol. wt. 236.3 M.f. C 9 H 16 N 8 COMMERCIALISATION: History Herbicide reported by R. A. Abbott & G. E. Barnsley (J. Sci. Food Agric., 1968, 19, 16). Evaluated by Shell Research Ltd. XMC Insecticide IRAC 1A; carbamate NOMENCLATURE: Common name XMC (JMAF) IUPAC name 3,5-xylyl methylcarbamate Chemical Abstracts name 3,5-dimethylphenyl methylcarbamate CAS RN [2655–14–3] Development codes H-69 (Hodogaya) Smiles code CNC(=O)Oc1cc(C)cc(C)c1 PHYSICAL CHEMISTRY: Composition Tech. grade is 97% pure. Mol. wt. 179.2 M.f. C 10 H 13 NO 2 Form Colourless crystals. M.p. 99 °C (tech.) B.p. 239.7 °C V.p. 6.88 mPa (25 °C) K ow logP = 2.3 (25 °C) Henry 2.33 × 10 –3 Pa m 3 mol –1 (25 °C, calc.) S.g./density 1.16 (20 °C) Solubility In water 0.53 g/l (25 °C). Soluble in most organic solvents; e.g. in acetone and ethanol >100, xylene 67 (all in g/l, 25 °C); also soluble in cyclohexanone and 3,5,5-trimethylcyclohex- 2-enone. Stability Rapidly hydrolysed in alkaline media. Relatively stable to neutral and weakly acidic aqueous solutions. Stable to light and to temperatures up to 90 °C. COMMERCIALISATION: History Introduced in 1968 as an insecticide by Hokko Chemical Industry Co., Ltd and Hodogaya Chemical Co., Ltd. Manufacturers Hodogaya; Saeryung APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Insecticide with predominantly contact action. Uses Control of leafhoppers and planthoppers on rice, and tea green leafhoppers on tea, at 600–1200 g/ha. Formulation types DP; EC; MG; WP. OCONHCH 3 CH 3 CH 3 Supplementary Entries – Extended XRD-563 553 PRODUCTS: Discontinued products ‘Cosban’* (Hodogaya); ‘Macbal’* (Hodogaya); ‘Maqbal’* (Hodogaya). ANALYSIS: Product analysis by hydrolysis to 3,5-xylenol, which is measured by uv spectroscopy. Residues determined by hydrolysis to 3,5-xylenol, a derivative of which is measured by glc. TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). EU Status (1107/2009) Never notifed to the EU. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats 542, rabbits 445, mice 245 mg/kg. Skin and eye Not a skin irritant (rabbits). Inhalation LC 50 for rats 1.02 mg/l. NOEL (90 d) for rats and mice 230 mg/kg b.w. daily. ADI/RfD 0.0034 mg/kg b.w. Toxicity Class WHO (a.i.) III EPA (formulation) III EC Classifcation Xn; R22 ECOTOXICOLOGY: Birds LD 50 (14 d) for quail 188, mallard ducks 1637 mg/kg. Fish LC 50 (48 h) for carp >40 mg/l. Daphnia EC 50 (3 h) for Daphnia pulex 0.055 mg/l. Algae EC 50 (72 h) 12.3 mg/l. Bees LD 50 (48 h, oral) 0.095 μg/bee; (48 h, contact) 0.53 μg/bee. Worms LD 50 (14 d) 45.4 mg/kg dry soil. ENVIRONMENTAL FATE: Animals In insects, metabolism mainly involves hydroxylation of the benzene ring and the ring methyl substituents. Soil/Environment In soil, hydrolysed to 3,5-xylenol and N-methylcarbamic acid. XRD-563 Fungicide NOMENCLATURE: IUPAC name 2,6-dichloro-N-(4-trifuoromethylbenzyl)benzamide Chemical Abstracts name 2,6-dichloro-N-[[4-(trifuoromethyl)phenyl] methyl]benzamide CAS RN [124426–49–9] Development codes XRD-563 Smiles code FC(F)(F)c1ccc(CNC(=O)c2c(Cl)cccc2Cl)cc1 PHYSICAL CHEMISTRY: Mol. wt. 348.2 M.f. C 15 H 10 Cl 2 F 3 NO Solubility In water 3.5 mg/l. Readily soluble in organic solvents, e.g. methanol and acetone. O NH CH 2 CF 3 Cl Cl 554 The Pesticide Manual Sixteenth Edition © BCPC 2012 xylachlor COMMERCIALISATION: History Reported by W. Arnold et al. (Proc. Br. Crop Prot. Conf. - Pests Dis., 1992, 1, 443). Fungicide evaluated by DowElanco. APPLICATIONS: Mode of action Can be applied as a foliar spray and penetrates into plant tissue very rapidly where it is transported acropetally. Shows curative, eradicant and protectant activity. Uses Control of powdery mildew on wheat and barley. Can be mixed with azole fungicides to give broad-spectrum control of cereal diseases. Formulation types EC. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for rats >5000, mice >500 mg/kg. Skin and eye Acute percutaneous LD 50 for rabbits >2000 mg/kg. Slight skin and eye irritation (rabbits). Other No evidence of teratogenicity and negative in the Ames test. ECOTOXICOLOGY: Birds Acute oral LD 50 for adult bobwhite quail >2000 mg/kg. Dietary LC 50 (8 d) >5000 ppm in diet. Fish LC 50 (96 h) for bluegill sunfsh >100, rainbow trout 50–100 mg/l. Daphnia LD 50 (24 h) >100 mg/l. xylachlor Herbicide NOMENCLATURE: Common name xylachlor (WSSA) IUPAC name 2-chloro-N-isopropylacet-2′,3′-xylidide Chemical Abstracts name 2-chloro-N-(2,3-dimethylphenyl)-N-(1-methylethyl)acetamide CAS RN [63114–77–2] Development codes AC 206 784 Smiles code CC(C)N(C(=O)CCl)c1cccc(C)c1C PHYSICAL CHEMISTRY: Mol. wt. 239.7 M.f. C 13 H 18 ClNO COMMERCIALISATION: History Herbicide evaluated by American Cyanamid Co. PRODUCTS: Discontinued products ‘Combat’* (Cyanamid). Supplementary Entries – Extended xylylcarb 555 xylylcarb Insecticide IRAC 1A; carbamate NOMENCLATURE: Common name xylylcarb (BSI, E-ISO, (m) F-ISO); MPMC (JMAF) IUPAC name 3,4-xylyl methylcarbamate Chemical Abstracts name 3,4-dimethylphenyl methylcarbamate CAS RN [2425–10–7] EC no 219–364–9 Development codes S-1046; S-21046 (both Sumitomo Chemical) Smiles code CNC(=O)Oc1ccc(C)c(C)c1 PHYSICAL CHEMISTRY: Mol. wt. 179.2 M.f. C 10 H 13 NO 2 Form Colourless solid. M.p. 79–80 °C; (tech., 71.5–76 °C) V.p. 121 mPa (25 °C) Solubility In water 580 mg/l (20 °C). In acetonitrile 930, cyclohexanone 770, xylene 134 (all in g/kg). Stability Hydrolysed in alkaline media. COMMERCIALISATION: History Insecticide reported by R. L. Metcalf et al. (J. Econ. Entomol., 1963, 56, 862). Introduced by Sumitomo Chemical Co., Ltd. Manufacturers Sumitomo Chemical APPLICATIONS: Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide. Uses Control of hoppers and other sucking insects on rice; and leafhoppers, planthoppers, and scale insects on fruit. Formulation types DP; EC; MG; WP. PRODUCTS: Discontinued products ‘Meobal’* (Sumitomo Chemical). ANALYSIS: Product analysis by hplc (S. Sakaue et al., Nippon Nogei Kagaku Kaishi, 1981, 55, 1237) or by uv spectrometry. Residues determined by glc of a derivative with ECD (J. Miyamoto et al., Nihon Hoyaku Gakkaishi, 1978, 3, 119). TOXICOLOGICAL & ENVIRONMENTAL REVIEWS: EHC 64 (1986; a review of carbamate pesticides in general). MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 375, female rats 325 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >1000 mg/kg. Toxicity Class WHO (a.i.) II EC Classifcation Xn; R22| N; R50, R53 OCONHCH 3 CH 3 CH 3 556 The Pesticide Manual Sixteenth Edition © BCPC 2012 zolaprofos ENVIRONMENTAL FATE: Animals Metabolism of carbamate insecticides is reviewed (M. Cool & C. K. Jankowski in Insecticides). zarilamid Fungicide NOMENCLATURE: Common name zarilamide ((m) F-ISO); zarilamid (BSI, E-ISO, not Brazil) IUPAC name (RS)-4-chloro-N-[cyano(ethoxy)methyl]benzamide Chemical Abstracts name (±)-4-chloro-N-(cyanoethoxymethyl)benzamide CAS RN [84527–51–5] unstated stereochemistry Development codes ICIA0001; PP001 Smiles code Clc1ccc(cc1)C(=O)NCOCCC#N PHYSICAL CHEMISTRY: Mol. wt. 238.7 M.f. C 11 H 11 ClN 2 O 2 Form Pale brown crystals. M.p. 111 °C V.p. 0.0047 mPa (20 °C) Henry 6.72 × 10 –6 Pa m 3 mol –1 (calc.) S.g./density 1.34 (25 °C) Solubility In water 167 mg/l (pH 5.3, 20 °C). In acetone >500, dichloromethane, methanol 271, ethyl acetate 336, hexane 0.12, toluene 26 (all in g/l, 20 °C). Stability Stable >0.75 y at ambient temperature; DT 50 (hydrolysis) 18 d (pH 5), 6 d (pH 7). COMMERCIALISATION: History Fungicide reported by S. P. Heaney et al. (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., 2, 551). Evaluated by ICI Agrochemicals. APPLICATIONS: Mode of action Anti-microtubular fungicide. MAMMALIAN TOXICOLOGY: Oral Acute oral LD 50 for male rats 526, female rats 775 mg/kg. Skin and eye Acute percutaneous LD 50 for rats >2000 mg/kg. Mild irritant to eyes. ECOTOXICOLOGY: Daphnia LC 50 5.65 mg/l. Bees LD 50 (contact) for honeybees >0.2 mg/bee. zolaprofos Insecticide IRAC 1B NOMENCLATURE: Common name zolaprofos (BSI, E-ISO, (m) F-ISO) IUPAC name O-ethyl S-3-methyl-1,2-oxazol-5-ylmethyl S-propyl phosphorodithioate; O-ethyl S-(3-methylisoxazol-5-ylmethyl) S-propyl phosphorodithioate Supplementary Entries – Extended zolaprofos 557 Chemical Abstracts name O-ethyl S-[(3-methyl-5-isoxazolyl)methyl] S-propyl phosphorodithioate CAS RN [63771–69–7] Development codes BAS 268I; BAS 26800-I (both BASF) Smiles code CCCSP(=O)(OCC)SCc1cc(C)no1 PHYSICAL CHEMISTRY: Mol. wt. 295.4 M.f. C 10 H 18 NO 3 PS 2 COMMERCIALISATION: History Insecticide evaluated by BASF AG. APPLICATIONS: Biochemistry Cholinesterase inhibitor.