Please Keep AbsolutelyConfidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited Solutions Manual December 2007 – last updated April 2013 1 Please Keep Absolutely Confidential 1 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 5 BrCH2 CH2Br 9 O CH3 C Cl2CH CH3 13 OH OH C CH3 CH3 CH3 2 2-butanone 1,2-dibromoethane pinacol 1,1-dichloroethane C4H8O C2H4Br2 C6H14O2 C2H4Cl2 CH3CH2 OH 6 10 O CH3 O O O 14 CH3 H CH3 CH3 OH O propionic acid 1,2-butanedione (biacetyl) C4H6O2 C3H6O2 O 3 CH3 4 O CH2CH3 7 CH2C N CH2C N 11 1,4-cyclohexanedione 2-propanol C6H8O2 C3H8O O 15 CH3 H CH3 Br ethyl acetate succinonitrile cyclopentanone 2-bromopropane C4H8O2 C4H4N2 C5H8O2 C3H7Br CH3O CH2CH3 O 8 12 CH3 CH3 CH3 C C CH3CH2 I 16 Cl Cl CH3 CH3 CH3 methyl propionate 2,2,3,3-tetramethylbutane iodoethane 1,4-dichlorobutane C4H8O2 C8H18 C2H5I C4H8Cl2 December 2007 – last updated April 2013 2 Please Keep Absolutely Confidential 17 Br ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 21 Br Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited H2N 25 COOH N CH2C 29 CH2 C CH3 O 1,3-dibromopropane 4-aminobutyric acid benzyl cyanide benzyl methyl ketone C3H6Br2 C4H9NO2 C8H7N C9H10O 18 19 Br 22 Cl 26 OCH3 CH2NH2 30 O 1-bromo-3-chloropropane anisole benzylamine propiophenone C3H6BrCl C7H8O C7H9N C9H10O Br N C 23 27 CH2OH OH 31 CH3 CH C H O 4-bromobutyronitrile benzyl alcohol 2-phenylethanol 2-phenylpropionaldehyde C4H6NBr C7H8O C8H10O C9H10O 28 + NH3 20 CH3 H COO 24 OH CH2Br 32 O H CH3 - alanine benzyl bromide 1-phenylethanol butyrophenone C3H7NO2 C7H7Br C8H10O C10H12O December 2007 – last updated April 2013 3 Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman O 33 O O 34 37 O Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited 41 N CH3 O C O 45 C O CH3 CH3 H CH3 O O H O t-butyl acetoacetate dibenzylamine propionic anhydride 1,1-diacetoxyethane C8H14O3 C14H15N C6H10O3 C6H10O4 CH3CH2 O C H 38 42 CH3 O N N CH3 CH3 O N,N,N,N-tetramethyl-1,2ethanediamine C6H16N2 C3H6O2 35 O O 39 H O COOCH3 CH3 diethyl oxalate dimethyl methylmalonate C6H10O4 C6H10O4 O 43 CH3 O O O 47 CH3 O CH3 CH3 O O O C C CH3OOC O CH3 ethyl formate 46 O C O OCH3 benzil 2,5-hexanedione ethylene glycol diacetate methyl acetyllactate C14H10O2 C6H10O2 C6H10O4 C6H10O4 36 O 40 CH3CH2O 44 CH3O OCH2CH3 48 O OCH3 O O O C C O O 1,2-diphenylethane diethyl carbonate dimethyl succinate diethyl succinate C14H14 C5H10O3 C6H10O4 C8H14O4 December 2007 – last updated April 2013 4 Please Keep Absolutely Confidential Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman O 49 O O 53 O 57 CHCl2 H3C CH3 H3C CH3 61 OCH3 OCH3 OCH3 ethylene glycol dipropionate α,α-dichlorotoluene 1,2,3-trimethoxybenzene durene C8H14O4 C7H6Cl2 C9H12O3 C10H14 CH3 50 51 O O C C O 54 58 OCH3 C H OCH3 CH3 62 CH3 CH3 CH3 CH3 butyric anhydride benzaldehyde dimethylacetal mesitylene 1,2,3,4-tetramethylbenzene C8H14O3 C9H12O2 C9H12 C10H14 Br 55 Br 59 OH 63 CH3 COOH CH3 CH3 CH3 CH3 CH3 52 CH3 CH3 1,4-dibromobenzene benzilic acid 1,2,3-trimethylbenzene 1,2,3,5-tetramethylbenzene C6H4Br2 C14H12O3 C9H12 C10H14 Br Br 56 60 OH CH3 CH3 OH CH3 64 CH3 CH3 CH3 CH3 CH3 CH3 4,4'-dibromobiphenyl catechol 1,2,4-trimethylbenzene hexamethylbenzene C12H8Br2 C6H6O2 C9H12 C12H18 December 2007 – last updated April 2013 5 Please Keep Absolutely Confidential 65 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 69 CH3 CH3 CH3 1,2,3,4,5,pentamethylcyclopentadiene C10H16 66 CH3 CH3 NH2 3-hydroxybutanone (acetoin) C4H8O2 70 74 NH2 HOOC COOH CH3 CH3 3,3-dimethylglutaric acid C7H12O4 78 HOOC COOH O acetamide 4-hydroxy-4-methyl-2pentanone C6H12O2 C2H5NO O HO CH3 CH3 2-methyl-2-butanol (t-amyl alcohol) C5H12O HO O 67 77 OH CH3 O CH3 H 73 OH CH3 CH3 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited 71 O O hexylamine 2,2-dimethylpentanedioc acid C7H12O4 C6H15N 75 CH3 O CH3CH2 O CH3 O 79 CH3 CH3 CH3 Br N N CH3 O ethyl glycolate isobutyl acetate ethyl 2-bromopropionate tetramethylurea C4H8O3 C6H12O2 C5H9O2Br C5H12N2O 68 72 O CH3CH2O C N OCH3 76 COOH O 80 O O OCH3 ethyl cyanoacetate 3,3-dimethylbutyric acid 4,4-dimethoxy-2-butanone 1,3-dioxan C5H7NO2 C6H12O2 C6H12O3 C4H8O2 December 2007 – last updated April 2013 6 Please Keep Absolutely Confidential 81 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Br 85 O 89 OH O 93 CH2 HO O H O 1,4-dioxan 2-bromohexanoic acid 2-methylbut-3-en-2-ol dibutyl ether C4H8O2 C6H11O2Br C5H10O C8H18O 82 O CN 86 O O 90 H - C H OH O O 94 + NH3 CH3 CN O O 83 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited O 18-crown-6 2-ethylmalononitrile threonine butylbenzene C12H24O6 C5H6N2 C4H9NO3 C10H14 H2C C CH2Cl 87 91 CN Br 95 Cl C(CH3)3 2,3-dichloropropene 3-methylbutyronitrile 1-bromo-3-phenylpropane t-butylbenzene C3H4Cl2 C5H9N C9H11Br C10H14 O 84 Cl O 88 H2N C C 92 H NO2 96 CH3 4-chlorobutyl acetate 5-amino-1-pentyne 1-nitropropane sec-butylbenzene C6H11O2Cl C5H9N C3H7NO2 C10H14 December 2007 – last updated April 2013 7 Please Keep Absolutely Confidential 97 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 101 C(CH3)3 105 O Cl C 109 O CH3O C CH3 HO CH2OCH3 CH3 neopentylbenzene p-chloroacetophenone 4-methoxyacetophenone 4-methoxymethylphenol C11H16 C8H7OCl C9H10O2 C8H10O2 98 CH2Cl 102 106 O CH3 CH3 C 110 O C O CH3 CH3 N C N Cl CH3 4-(n-butyl)-α-chlorotoluene p-toluyl chloride p-cresyl acetate 4-dimethylaminobenzonitrile C11H15Cl C8H7OCl C9H10O2 C9H10N2 99 O 103 CH3O 107 COOH O H3C 111 C CH3 Br N CH3 OCH3 4-methyl-4-phenyl-2-pentanone C12H16O 100 O Br C 104 p-anisic acid methyl p-toluate p-bromo-N,N-dimethylaniline C8H8O3 C9H10O2 C8H10NBr CH2O C CH3 108 CH3O CH2OH O CH3 112 O CH3O C C(CH3)3 p-bromoacetophenone benzyl acetate p-methoxybenzyl alcohol p-anisyl t-butyl ketone C8H7OBr C9H10O2 C8H10O2 C12H16O2 December 2007 – last updated April 2013 8 Please Keep Absolutely Confidential 113 O (H3C)3C Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 117 121 O O C CH3 CH3CH2O H C NH2 125 N O NO2 114 115 o-nitrobenzaldehyde ethyl p-aminobenzoate C12H16O2 C7H5NO3 C9H11NO2 (CH3)3C C OCH3 O H C 122 OCH3 CH3CH2O C O NH2 p-ethoxybenzamide C12H16O2 C8H8O2 C9H11NO2 119 p-ethoxyacetanilide (phenacetin) C10H13NO2 H 126 HO N C CH3 O 4-methoxybenzaldehyde NO2 O2N C C H 123 p-hydroxyacetanilide (paracetamol) C8H9NO2 127 O CH3 C CH3 O O methyl 4-t-butylbenzoate CH3O C CH3CH2O 4-t-butylphenyl acetate 118 H O C NH2 O O 116 H p-nitroanisole 4-nitrophenylacetylene 4-aminoacetophenone ethyl p-ethoxybenzoate C7H7NO3 C8H5NO2 C8H9NO C11H14O3 C NO2 120 124 O C O O C H3C OH O CH3 NH C CH3 CH3O O OCH3 O p-nitrobenzaldehyde 4-acetoxybenzoic acid 4-methylacetanilide C7H5NO3 C9H8O4 C9H11NO December 2007 – last updated April 2013 128 9 methyl (p-methoxyphenyl)propionionate C11H14O3 Please Keep Absolutely Confidential 129 H N Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 133 O O 137 O C O O O C 141 H O O CH3 C O 130 N-isopropylbenzylamine hydroquinone dipropionate C10H15N C12H14O4 OCH3 O O 134 C CH3 131 NCO O cyclopropyl methyl ketone C5H8O 142 CH3O C O methyl 2-methoxy-2phenylacetate C10H12O3 138 O O 1,3-dihydroxyphenyl dipropionate C12H14O4 C C H OCH3 OH C O O O diethyl terephthalate dimethyl o-phthalate cyclopropane carboxylic acid C12H14O4 C10H10O4 C4H6O2 O 135 C C 139 O O O 143 H C O O 132 phenyl isocyanate diethyl o-phthalate cycloheptanone benzoylcylopropane C7H5NO C12H14O4 C7H12O C10H10O OCH3 136 O OCH3 H O C 140 O C 144 H CH2 C O OCH2CH3 O phenylacetaldehyde dimethyl acetal C10H14O2 December 2007 – last updated April 2013 diethyl isophthalate cycloheptatriene ethyl cyclobutanecarboxylate C12H14O4 C7H8 C7H12O2 10 Please Keep Absolutely Confidential 145 C(CH3)3 O Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 149 153 157 CH3 (CH3)3C O OH O C O NEt2 (CH3)3C 4-t-butylcyclohexanone benzyl benzoate N,N-diethyl-m-toluamide 3,5-di-t-butylphenol C10H18O C14H12O2 C12H17NO C14H22O 146 150 H O CH3 154 158 Br Br N H3C O N-methylacetamide H2N NH2 Br (p-cresyl)methyl phenyl ketone C15H14O2 C3H7NO 147 OH O CH3 151 CH3 O 2-bromophenol 3,5-dibromocumene C6H5OBr C9H10Br2 155 159 O Br O C CH3 O COOH 148 1,4-diaminobutane ** p-cresyl phenylacetate C4H12N2 C15H14O2 H2N NH2 152 Cl3C COOH acetylsalicylic acid (aspirin) C9H8O4 156 CCl3 160 NH2 Br 3-bromo-5-isopropylbenzoic acid C10H11O2Br Br O O H O 1,5-diaminopentane ** C5H14N2 December 2007 – last updated April 2013 1,3-bis(trichloromethyl)benzene C8H4Cl6 11 2,6-dibromoaniline piperonal C6H5NBr2 C8H6O3 Please Keep Absolutely Confidential 161 162 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 165 CH3 CH3 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited 169 O NO2 173 O 3-nitro-o-xylene 2-cyclohexene-1-one indane α-tetralone C8H9NO2 C6H8O C9H10 C10H10O Cl CH3 Cl Cl 166 170 O 174 O OH O 2,4,5-trichlorotoluene 2-hydroxycyclohex1-en-3-one C6H8O2 C7H5Cl3 163 Cl NH2 Cl Cl 167 171 O C CH3 3,3-dimethylindan-1-one β-tetralone C11H12O C10H10O 175 O H 164 CH3 2,4,5-trichloroaniline 1-acetyl-1-cylohexene 1-indanone 9-methylfluorene C6H4NCl3 C8H12O C9H8O C14H12 CH3O I OCH3 I 168 172 CH3 176 O CH3 O O CH3 4,6-diiodo-1,3dimethoxybenzene C8H8O2I2 December 2007 – last updated April 2013 4-methylpent-3-en-2-one (mesityl oxide) C6H10O 12 2-indanone fluorenone C9H8O C13H8O Please Keep Absolutely Confidential 177 O CH3 CH3 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 181 CH3CH2 O O O 183 N CH3 HO C C C C6H10O3 December 2007 – last updated April 2013 CH3 C C C CH2CH3 OH H 187 C C C OH CH3 COOH H CH3 3-methyl-1-phenylpent1-yn-3-ol C12H14O C C CH3 2-hydroxy-3-methylbutyric acid C5H10O3 191 OH H C mevalonic lactone C3H6Br2 CH2 CH CH2 OH OH OH CH3 CH3 184 O 1,2-dibromopropane 190 CH3 CH3 2,5-dimethyl-3-hexyne2,5-diol C8H14O2 C O (Z)-1-methoxybut1-en-4-yne C5H6O CH3 CH3 O OH CH3 CH2Br H 1,2,2,6,6-pentamethylpiperidine C10H21N 2,2-dimethylglutaric anhydride C7H10O3 180 CH3 CH3 CH3 O Br H 186 CH3 CH3 3,3-dimethylglutaric anhydride C7H10O3 CH3 O 182 O 179 OCH3 C 4-ethyl-4-methyl-2,6piperidinedione C8H13NO2 O CH3 N 189 H 2,4,6-trimethyl1,3,5-trioxane C6H12O3 CH3 H C CH3 O H 185 CH3 O 178 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited H 1-phenyl-1,3-pentadiyne glycerol C11H8 C3H8O3 COOCH3 188 192 OH CH3 O C H HC (Z)-3-methylpent-2en-4-ynal C6H6O C NH2 CH methyl 4-amino-3,5diethynylbenzoate C12H9NO2 13 CH3 H 2-butanol C4H10O Please Keep Absolutely Confidential 193 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 197 O Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited S NH2 O 201 O S Cl 205 H NH2 O O p-aminobenzenesulfonamide C6H8N2O2S dibenzyl sulfoxide C14H14OS vinyl 2-chloroethyl ether cinnamaldehyde C4H7OCl C9H8O 198 194 O S 202 S 206 N O COOH O CH2OH CH3 O (E)-3-(phenylthio)acrylic acid C9H8O2S 195 N-(p-tolyl)succinimide cinnamyl alcohol C4H6O2S C11H11NO2 C9H10O 199 O CH3 divinyl sulfone S OCH2CH3 207 Cl H H CH C(CH3)3 O H ethyl p-toluenesulfonate allyl p-anisyl thioether C9H12O3S O 200 O (E)-3-chloro-4,4-dimethyl-1phenyl-1-pentene C13H17Cl phenylacetaldeyde ethylene glycol acetal C10H12O2 C10H12OS O CH3 O CH2 CH3O O 196 203 S O S O CH2CH2O 4 S CH3 204 S CH(CH3)2 208 H H O O CH3 Br CH3 p-tolyl methyl sulfoxide C8H10OS December 2007 – last updated April 2013 (E)-1-phenyl-4-methyl-1penten-3-one C12H14O tetraethylene glycol ditosylate C22H30O9S2 14 (Z)-β-bromostyrene C8H7Br Please Keep Absolutely Confidential 209 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman H 213 H NO2 Br 217 C Cl Cl 1,1-di-(p-chlorophenyl)-2,2,2trichloroethane (DDT) C14H9Cl5 (E)-p-nitro-β-bromostyrene C8H6BrNO2 OH O Cl 214 Cl 3-benzyloxy-1-propanol COOH 211 215 O2N CH3O O 219 Br Br 216 CH3O 5,6-dimethoxy-2coumaranone C10H10O4 December 2007 – last updated April 2013 malonaldehyde dimethyl acetal C7H16O4 OCH2CH3 222 H CN CH3 H Cl OCH2CH3 O OCH3 O CH2 CH2 HO OCH3 C H CH2 O CH2 methyl (E)-3-methylacrylate 1,3-dibenzylglycerol C5H8O2 C17H20O3 220 CH3 2-chloroacetaldehyde diethylacetal C6H13O2Cl 223 224 O CH3O OCH3 OCH2CH3 O H methyl 2,3-dibromo-3(p-nitrophenyl)propionate C10H9NO4Br2 C9H8O4 CH3O OCH3 OCH3 4-cyano-2,2dimethylbutyraldehyde C7H11NO O homophthallic acid 221 O COOH 212 218 COOH 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) C8H5O3Cl3 C10H14O2 OCH2CH3 diethyl isopropylidenemalonate C10H16O4 O Cl O CH3 CH3 CCl3 H 210 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited N CN OCH3 2,3-di-(p-anisyl)butyronitrile 2,5-dimethyl-2,4-hexadiene pyridine C18H19NO2 C8H14 C5H5N 15 Please Keep Absolutely Confidential Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman O 225 N H3C 229 233 O CH3 C 237 C O O C H CH(CH3)2 N C O2N CH(CH3)2 S O C O 4-picoline isopropyl nicotinate citraconic anhydride C6H7N C9H11NO2 C5H4O3 226 CH3 230 N 227 234 CH3 N 2-(5-nitrothienyl) isopropyl ketone C8H9NO3S 238 COOH O NH2 H CH3 N N 2-picoline 2-methyl-6-aminopyridine 2-furoic acid 4-methylimidazole C6H7N C6H8N2 C5H4O3 C4H6N2 231 CH3 235 N N H3C C(CH3)3 O N 239 S O 3-picoline 4-methylpyrimidine 2-furyl t-butyl ketone benzothiophene C6H7N C5H6N2 C9H12O2 C8H6S 228 232 O C 236 H O CH3 O2N 240 S NO2 N N H 3-acetylpyridine styrene epoxide 2,4-dinitrothiophene 2,3,4,9-tetrahydrocarbazole C7H7NO C8H8O C4H2N2O4S C12H13N December 2007 – last updated April 2013 16 Please Keep Absolutely Confidential 241 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 245 CH3 249 O O Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited O N CH3 α-angelicalactone octahydroanthracene N-methylmorpholine C5H6O2 C14H18 C5H11NO OH 253 N(CH3)2 HO N,N-dimethyl-2,3-dihydroxy1-propylamine C5H13NO2 O 242 246 O CH3 O O N OH CH3 anthraquinone cyclopentanone oxime pseudoephedrine C14H8O2 C5H9NO C10H15NO 247 OH 251 H 255 N O N H 244 H CH3 O 2-methyltetrahydrofuran-3-one C5H8O2 243 254 N H O OH 250 C(CH3)3 butyrolactone dodecahydrotriphenylene cyclohexanone oxime t-butylformamide C4H6O2 C18H24 C6H11NO C5H11NO CH3 CH3 O O CH3 248 N CH3 tetramethyl-1,3cyclobutanedione C8H12O2 December 2007 – last updated April 2013 O 252 256 H HS CH2 CH H N COOH C O triphenylene ε-caprolactam N-acetylcysteine C18H12 C6H11NO C5H9NO3S 17 CH3 Please Keep Absolutely Confidential 257 HO ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman O 261 OH 265 269 OH CH3 CH3 H CH CH2NH CH3 HO Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited O HO H OH CH3 H C O OH CH3 N H O adrenalin 3-methylbutyraldehyde 2-methyl-2,4-pentanediol N-acetylglutamic acid C9H13NO3 C5H10O C6H14O2 C7H11NO5 258 N H CH2 CH COO+ NH3 262 CH2 CH OCH3 266 OCH2CH3 CH 270 OH OCH2CH3 H HO O OCH2CH3 CH3 N H O tryptophan acrolein diethyl acetal eugenol N-acetyltyrosine ethyl ester C11H12N2O2 C7H14O2 C10H12O2 C13H17NO4 259 263 H N S O C C H 271 O C (CH3)3C O HO C CH2CH2 CH COOH O NH2 C C CH3 N-acetylhomocysteine thiolactone C6H9NO2S 260 Cl H 267 NH2 E -1-chloro-4-(4-tbutylphenyl)but-1-en-3-yne C14H15Cl allylamine C3H7N 264 268 H HO O OH CH3 N C4H6O 272 O H 2,5-dihydrofuran O O glutamic acid adamantine N-acetylaspartic acid 2,3-dihydrofuran C5H9NO4 C10H16 C6H9NO5 C4H6O December 2007 – last updated April 2013 18 Please Keep Absolutely Confidential COOH 273 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 277 O 281 Cl O N C COOH O CH2CH3 2,3-naphthalenedicarboxylic acid C12H8O4 274 OCH3 ethyl 4-piperidone-Ncarboxylate C8H13NO3 2-chloronaphthalene C10H7Cl 278 COOH CH3 N C O H 282 NO2 sec-butylbenzene 1-methoxy-4-nitronaphthalene C11H9NO3 CH3 275 N-acetyl-2-amino-4-phenyl(E)-but-2-enoic acid C12H13NO3 C10H14 279 CH3 O 283 CH3O O N H CH3 CH3 OCH3 N-(1-methyl-1-phenylethyl)butyramide C12H17NO 1,5-dimethylnaphthalene C12H12 276 CH3 280 CH3 1,3-dimethylnaphthalene C12H12 December 2007 – last updated April 2013 O OCH2CH3 O OCH2CH3 diethyl 2-(1,1dimethylheptyl)malonate C16H30O4 19 OH 3-hydroxy-3-methyl-5,8dimethoxy-1-coumarinone C13H16O4 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Chapter 9.2 – The Analysis of MixturesProblem 284 Problem 286 Problem 284 Compound Mole % ethanol 57 bromoethane Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited Compound Mole % benzene 24 ethyl acetate 59 dioxane 17 Compound Mole % ethanol 41 bromoethane 59 43 Problem 285 Compound Mole % benzene 15 diethyl ether dichoromethane December 2007 – last updated April 2013 Problem 287 46 39 20 Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Problem 288 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited Problem 290 Compound Mole % Compound Mole % benzene 13 fluorene 75 diethyl ether 22 fluorenone 25 dichoromethane 65 Compound Mole % 4-nitroanisole 38 2-nitroanisole 62 Problem 291 Problem 289 Compound Mole % benzene 23 ethyl acetate 51 dioxane 26 December 2007 – last updated April 2013 21 Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Chapter 9.3 – Problems in 2D NMR Problem 292 Proton H1 H2 H3 H4 1-propanol Chemical Shift (δ) in ppm 3.49 1.50 0.85 2.95 Problem 293 Problem 294 Carbon C1 C2 C3 Chemical Shift (δ) in ppm 64.0 25.5 9.9 1-iodobutane December 2007 – last updated April 2013 22 isobutanol Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited Please Keep Absolutely Confidential Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Problem 295 Problem 297 1 3-heptanone CH3 2 3 4 5 CH2 C CH2 CH2 6 CH2 4 7 1-bromobutane CH3 3 CH3 2 CH2 1 CH2 CH2 Br O Proton Chemical Shift (δ) in ppm H1 0.91 H2 1.94 H4 1.97 H5 1.44 H6 1.14 H7 0.79 Proton Carbon H1 Chemical Shift (δ) in ppm 3.39 C1 Chemical Shift (δ) in ppm 33.4 H2 1.82 C2 34.7 H3 1.45 C3 21.4 H4 0.91 C4 13.2 Problem 298 1 3-octanone 2 CH3 CH2 3 C 4 5 CH2 CH2 6 CH2 7 CH2 8 CH3 O 3 5 δ-valerolactone Proton 2 4 Problem 296 Chemical Shift (δ) in ppm Proton O O Carbon C1 Chemical Shift (δ) in ppm 170.0 H2 2.08 C2 29.9 H3 1.16 C3 19.0 H4 1.08 C4 22.2 H5 3.71 C5 68.8 December 2007 – last updated April 2013 Carbon H1 Chemical Shift (δ) in ppm 0.92 C1 Chemical Shift (δ) in ppm 7.8 H2 1.92 C2 35.4 C3 209.0 1 23 H4 1.94 C4 42.1 H5 1.47 C5 23.7 H6 1.11 C6 31.7 H7 1.19 C7 22.7 H8 0.82 C8 14.0 Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Problem 299 Problem 300 c b a a COOCH2CH3 d diethyl diethylmalonate e f g CH3CH2 C butyl ethyl ether h CH2 c O CH2 d e f CH2 CH2 CH3 Ha Chemical Shift (δ) in ppm 1.11 Hb 3.29 Cb 66.0 Hc 3.27 Cc 70.1 Ca Chemical Shift (δ) in ppm 14.0 Hd 1.52 Cd 32.1 Cb 60.8 He 1.36 Ce 19.4 Cc 171.9 Hf 0.87 Cf 13.5 i Carbon Ha Chemical Shift (δ) in ppm 1.19 Hb 4.13 Proton j k Hd 0.76 Cd 8.1 He 1.88 Ce 24.5 Cf 58.0 Hg 1.88 Cg 24.5 Hh 0.76 Ch 8.1 Ci 171.9 Hj 4.13 Cj 60.8 Hk 1.19 Ck 14.0 December 2007 – last updated April 2013 CH3 b CH2CH3 COOCH2CH3 Proton Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited 24 Carbon Ca Chemical Shift (δ) in ppm 15.0 Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Problem 301 Problem 302 1-iodobutane butyl butyrate Proton Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited Carbon Ha Chemical Shift (δ) in ppm 0.75 Ca Chemical Shift (δ) in ppm 13.9 Hb 1.19 Cb 19.5 Hc 1.40 Cc 31.2 Hd 3.97 Cd 64.0 Ce 172.8 Hf 2.08 Cf 36.2 Hg 1.52 Cg 19.0 Hh 0.79 Ch 13.9 December 2007 – last updated April 2013 1-butanol 1-iodobutane 25 1 4 3 2 1 CH3 CH2 CH2 CH2 4 3 2 1 CH3 CH2 CH2 CH2 OH I 1 1-butanol H1 H Chemical Shift (δ) in ppm 2.70 H1 H Chemical Shift (δ) in ppm 3.41 H2 1.40 H2 1.27 H3 1.08 H3 1.39 H4 0.64 H4 0.84 -OH 1.95 Please Keep Absolutely Confidential Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Problem 303 Problem 304 CH3 (E)- and (Z)-2-butene H C (Z)-3-methyl-2-penten-4-ynol C CH2OH C C H H Problem 305 Br C C CH3 CH3 H8 NO2 H2 H7 1-nitronaphthalene H3 H6 H5 H CH3 C CH3 December 2007 – last updated April 2013 C Br 26 H4 Proton Chemical Shift (δ) in ppm H2 8.22 H3 7.53 H4 8.10 H5 7.95 H6 7.62 H7 7.71 H8 8.56 Please Keep Absolutely Confidential Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Problem 306 Problem 309 COOCH2CH3 CH3 ethyl diethylmalonate CH3CH2 C geraniol COOCH2CH3 H CH3 HOCH2 Problem 307 butyl valerate CH3 CH2 CH2 CH2 O C CH2 CH2 CH2 CH3 O Problem 308 CH3 CH3 H nerol CH3 H December 2007 – last updated April 2013 CH3 H CH2OH 27 H Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited Chapter 9.4 – Analysis of NMR Spectra Problem 310 Problem 311 Structure Number of 1H environments Number of 13C environments CO CH2CH2CH3 4 5 CH3CH2 CO CH2CH3 2 3 CH2 CHCH2CH3 5 4 cis- C H 3 C H C H C H 3 2 2 trans- CH3CH CHCH3 2 2 1 1 3 4 2 3 3 4 1 2 2 4 5 7 slow chairchair 2 1 fast chairchair 1 1 rigid 7 4 CH3 Cl Chemical Shifts Br δA = 300 Hz / 60 MHz = 5.0 ppm δM = 240 Hz / 60 MHz = 4.0 ppm δX = 120 Hz / 60 MHz = 2.0 ppm Br Cl Cl Br Br Br Cl Cl Problem 312 OCH3 Chemical Shifts H Cl December 2007 – last updated April 2013 28 δA = 180 Hz / 200 MHz = 0.90 ppm δM = 220 Hz / 200 MHz = 1.10 ppm δX = 300 Hz / 200 MHz = 1.50 ppm Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Problem 313 Problem 314 Spin System Chemical Shifts Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited A2X3 δA = 150 Hz / 400 MHz = 0.375 ppm δX = 300 Hz / 400 MHz = 0.750 ppm Chemical Shifts δA = 3.36 ppm = 3.36 x 60 = 202 Hz from TMS δX = 1.11 ppm = 1.11 x 60 = 67 Hz from TMS 1st Order Analysis ∆νAX = νA - νX = 202 - 67 = 135 Hz ∆νAX / JAX = 135 / 7 = 19.3 st This ratio is much greater than 3 so a 1 order analysis is justified. December 2007 – last updated April 2013 29 Please Keep Absolutely Confidential Problem 315 Spin System Chemical Shifts Coupling constants 1st Order Analysis Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AMX Problem 316 Spin System AMX δA = 501 Hz / 100 MHz = 5.01 ppm δM = 439 Hz / 100 MHz = 4.39 ppm δX = 408 Hz / 100 MHz = 4.08 ppm Chemical Shifts JAM = 3.1 Hz JAX = 20.1 Hz JMX = 1.1 Hz δA = 460 Hz / 60 MHz = 7.67 ppm δX = 442 Hz / 60 MHz = 7.37 ppm δM = 394 Hz / 60 MHz = 6.57ppm Coupling constants JAM = 1.70 Hz JAX = 0.85 Hz JMX = 3.65 Hz 1st Order Analysis ∆νΑΜ = νA - νM = 460 - 394 = 66 Hz ∆νΑΞ = νA - νX = 460 - 442 = 18 Hz ∆νΜΞ = νM - νX = 442 - 394 = 48 Hz ∆νΑΜ / JAM = 66 / 1.7 = 38.8 ∆νΑΞ / JAX = 18 / 0.85 = 21.2 ∆νΜΞ / JMX = 48 / 3.65 = 13.2 ∆νΑΜ = νA - νM = 501 - 439 = 62 Hz ∆νΑΞ = νA - νX = 501 - 408 = 93 Hz ∆νΜΞ = νM - νX = 439 - 408 = 31Hz ∆νΑΜ / JAM = 62 / 3.1 = 20.0 ∆νΑΞ / JAX = 93 / 20.1 = 4.6 ∆νΜΞ / JMX = 31 / 2.1 = 14.7 st All ratios are greater than 3 so a 1 order analysis is justified. st All ratios are greater than 3 so a 1 order analysis is justified. December 2007 – last updated April 2013 30 Please Keep Absolutely Confidential Problem 317 Spin System ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AMX Chemical Shifts δ3 = 673 Hz / 100 MHz = 6.73 ppm δ4 = 719 Hz / 100 MHz = 7.19 ppm δ6 = 777 Hz / 100 MHz = 7.77ppm Coupling constants 3 1st Order Analysis ∆ν34 = ν4 - ν3 = 719 - 673 = 46 Hz ∆ν46 = ν6 - ν4 = 777 - 719 = 58 Hz ∆ν36 = ν6 - ν3 = 777 - 673 = 104 Hz ∆ν34 / J34 = 46 / 8.8 = 5.2 ∆ν46 / J46 = 58 / 2.3 = 25.2 ∆ν36 / J36 = 104 / <1 = >104 Problem 318 J34 = 8.8 Hz J46 = 2.3 Hz 5 J36 not resolved (< 1Hz) Spin System Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited AMX Chemical Shifts δA = 628 Hz / 100 MHz = 6.28 ppm δB = 527 Hz / 100 MHz = 5.27 ppm δC = 592 Hz / 100 MHz = 5.92 ppm Coupling constants JAB = 2.1 Hz; JAC = 17.5 Hz; JBC = 9.9 Hz 1st Order Analysis ∆νAB = νA - νB = 628 - 527 = 101 Hz ∆νAC = νA - νC = 628 - 592 = 36 Hz ∆νBC = νC - νB = 592 - 527 = 65 Hz ∆νAB / JAB = 101 / 2.1 = 48.1 ∆νAC / JAC = 36 / 17.5 = 2.1 ∆νBC / JBC = 65 / 9.9 = 6.6 4 st All ratios are greater than 3 so a 1 order analysis is justified. December 2007 – last updated April 2013 st 2 out of 3 ratios are greater than 3 so this is borderline 1 order. The main st st deviation from 1 order is that intensities are severely distorted - a 1 order spectrum would have all lines of equal intensity. JAC = 17.5 Hz indicates that HA and HC must be trans. JBC = 9.9 Hz indicates HA and HC are cis. 31 Please Keep Absolutely Confidential Problem 319 Spin System Chemical Shifts Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AX3 Problem 320 Spin System AX3 δA = 160 Hz / 60 MHz = 2.67 ppm δX = 280 Hz / 60 MHz = 4.67 ppm Chemical Shifts δA = 199 Hz / 100 MHz = 1.99 ppm δX = 99 Hz / 100 MHz = 0.99 ppm Coupling constants JAX = 5 Hz 1st Order Analysis ∆νAX = νA - νX = 199 - 99 = 100 Hz ∆νAX / JAX = 100 / 5 = 20.0 ∆νAX / JAX is much greater than 3 so a 1 order analysis is justified. st December 2007 – last updated April 2013 32 Please Keep Absolutely Confidential Problem 321 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 4 Spin System AMX2 Chemical Shifts Problem 322 δA = 340 Hz / 60 MHz = 5.67 ppm δM = 240 Hz / 60 MHz = 4.00 ppm δX = 100 Hz / 60 MHz = 1.67 ppm December 2007 – last updated April 2013 4 Spin System AM2X Chemical Shifts 33 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited δA = 110 Hz / 60 MHz = 1.83ppm δM = 200 Hz / 60 MHz = 3.33 ppm δX = 290 Hz / 60 MHz = 4.83 ppm Please Keep Absolutely Confidential Problem 323 4 Spin System Chemical Shifts Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AM2X Problem 324 4 Spin System δA = 646 Hz / 100 MHz = 6.46 ppm δM = 510 Hz / 100 MHz = 5.10 ppm δX = 395 Hz / 100 MHz = 3.95 ppm Coupling constants JAM = 3 Hz; JAX = 16 Hz; JMX = 5 Hz; 1st Order Analysis ∆νAX = νA - νX = 646 - 395 = 251 Hz ∆νAM = νA - νM = 646 - 510 = 136 Hz ∆νMX = νM - νX = 510 - 395 = 115 Hz ∆νAX / JAX = 251 / 16 = 15.7 ∆νAM / JAM = 136 / 3 = 45.3 ∆νMX / JMX = 115 / 5 = 23.0 A2MX Chemical Shifts δA = 279 Hz / 100 MHz = 2.79 ppm δM = 149 Hz / 100 MHz = 1.49 ppm δX = 39 Hz / 100 MHz = 0.39 ppm Coupling constants JAM = 4.5 Hz; JAX = 7.5 Hz; JMX = 11.0 Hz; 1st Order Analysis ∆νAX = νA - νX = 279 - 39 = 240 Hz ∆νAM = νA - νM = 279 - 149 = 130 Hz ∆νMX = νM - νX = 149 - 39 = 110 Hz ∆νAX / JAX = 240 / 7.5 = 32.0 ∆νAM / JAM = 130 / 4.5 = 28.9 ∆νMX / JMX = 110 / 11 = 10.0 st All ratios are significantly greater than 3 so a 1 order analysis is justified. st All ratios are significantly greater than 3 so a 1 order analysis is justified. December 2007 – last updated April 2013 34 Please Keep Absolutely Confidential Problem 325 4 Spin System Chemical Shifts Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AMX2 Problem 326 5 Spin System δA = 302 Hz / 100 MHz = 3.02 ppm δM = 160 Hz / 100 MHz = 1.60 ppm δX = 37 Hz / 100 MHz = 0.37 ppm Coupling constants JAM = 12.0 Hz; JAX = 5.0 Hz; JMX = 8.0 Hz; 1st Order Analysis ∆νAX = νA - νX = 302 - 37 = 265 Hz ∆νAM = νA - νM = 302 - 160 = 142 Hz ∆νMX = νM - νX = 160 - 37 = 123 Hz ∆νAX / JAX = 265 / 5.0 = 53.0 ∆νAM / JAM = 142 / 12.0 = 11.8 ∆νMX / JMX = 123 / 8.0 = 15.4 A2M2X Chemical Shifts δA = 1000 Hz / 200 MHz = 5.0 ppm δM = 500 Hz / 200 MHz = 2.5 ppm δX = 100 Hz / 200 MHz = 0.5 ppm Coupling constants JAM = 3.0 Hz; JAX = 7.0 Hz; JMX = 10.0 Hz; 1st Order Analysis ∆νAX = νA - νX = 1000 - 100 = 900 Hz ∆νAM = νA - νM = 1000 - 500 = 500 Hz ∆νMX = νM - νX = 500 - 100 = 400 Hz ∆νAX / JAX = 900 / 7.0 = 128.6 ∆νAM / JAM = 500 / 3.0 = 166.7 ∆νMX / JMX = 400 / 10.0 = 40.0 st All ratios are significantly greater than 3 so a 1 order analysis is justified. st All ratios are significantly greater than 3 so a 1 order analysis is justified. December 2007 – last updated April 2013 35 Please Keep Absolutely Confidential Problem 327 5 Spin System ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AMX3 Chemical Shifts δA = 710 Hz / 100 MHz = 7.10 ppm δM = 585 Hz / 100 MHz = 5.85 ppm δX = 192 Hz / 100 MHz = 1.92 ppm Coupling constants JAM = 15.3 Hz; JAX = 6.9 Hz; JMX = 1.6 Hz; 1st Order Analysis ∆νAX = νA - νX = 710 - 192 = 518 Hz ∆νAM = νA - νM = 710 - 585 = 125 Hz ∆νMX = νM - νX = 585 - 192 = 393 Hz ∆νAX / JAX = 518 / 6.9 = 84.7 ∆νAM / JAM = 125 / 15.3 = 8.2 ∆νMX / JMX = 393 / 1.6 = 245.6 st All ratios are significantly greater than 3 so a 1 order analysis is justified. JAM = 15.3 Hz is typical of a coupling between vinylic protons which are trans to each other (see Section 5.7) December 2007 – last updated April 2013 36 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited Please Keep Absolutely Confidential Problem 328 5 Spin System Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman ADMX3 1st Order Analysis ∆νAD = νA ∆νAM = νA ∆νAX = νA ∆νDM = νD ∆νDX = νD ∆νMX = νM- νD = 956 - 695 = 261 Hz νM = 956 - 619 = 337 Hz νX = 956 - 205 = 751 Hz νM = 695 - 619 = 76 Hz νX = 695 - 205 = 490 Hz νX = 619 - 205 = 414 Hz ∆νAD / JAD = 261 / <1 = >261 ∆νAM / JAM = 337 / 8.2 = 41.1 ∆νAX / JAX = 751 / <1 = >751 ∆νDM / JDM = 76 / 15.8 = 4.8 ∆νDX / JDX = 490 / 6.9 = 71.0 ∆νMX / JMX = 414 / 1.6 = 258.8 st All ratios are significantly greater than 3 so a 1 order analysis is justified. The critical coupling constant is JDM = 15.8 Hz which is typical of a coupling between vinylic protons which are trans to each other (see Section 5.7). The compound is: O H Chemical Shifts Coupling constants δA = 956 Hz / 100 MHz = 9.56 ppm; δD = 695 Hz / 100 MHz = 6.95 ppm; δM = 619 Hz / 100 MHz = 6.19 ppm; δX = 205 Hz / 100 MHz = 2.05 ppm; December 2007 – last updated April 2013 M 37 H C H JAD= < 1 Hz; JAM = 8.2 Hz; JAX = < 1 Hz; JDM = 15.8 Hz; JDX = 6.9 Hz; JMX = 1.6Hz; D C A C CH3 X Please Keep Absolutely Confidential Problem 329 ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 5 Spin System AMX3 Chemical Shifts Problem 330 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited 3 Spin System A2X δA = 80 Hz / 60 MHz = 1.33 ppm δM = 220 Hz / 60 MHz = 3.67 ppm δX = 320 Hz / 60 MHz = 5.33 ppm Of the 6 isomeric anilines, only compounds 4 and 6 have the correct symmetry to give a spectrum with only two chemical shifts in the aromatic region, in the ratio 2:1. Both 4 and 6 would give A2X spin systems. The measured coupling constant is 7.7 Hz which is in the range for protons which are ortho to each other. Compound 4 is the correct answer. December 2007 – last updated April 2013 38 NH2 Br Br HA HA HX Please Keep Absolutely Confidential Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Problem 331 Problem 332 1 All of the protons in the H spectrum 1,5-dichoronaphthalene have protons which are ortho to them. This means that every proton must have at least one large (>7 Hz) ortho coupling. The spectrum has one proton (at δ 7.1) which has only a small coupling so this cannot be the spectrum of 1,5-dichloronaphthalene. The spectrum is obtained after D2O exchange so the carboxylic acid and phenolic protons will not be present and the spectrum only contains the aromatic and vinylic protons. The spectrum shows 6 distinct resonances therefore compounds 5 and 6 can be eliminated because they would each have only 4 resonances (on symmetry grounds). The spectrum is an AMX spectrum with couplings between A and X of about 8.3 Hz (typical of an ortho coupling) and coupling between M and X of about 2.7 Hz (typical of a meta coupling). Two possible structure are given below. The proton at about δ 7.1 shows no large coupling (> 7 Hz), this means that it has no protons ortho to it. This eliminates compounds 1 and 2 since all protons in these compounds will have at least one large ortho coupling. Compounds 3 and 4 differ by the stereochemistry at the double bond. The proton at δ 6.4 is clearly one of the vinylic protons and it is coupled to the other vinylic proton at δ 7.6. The coupling constant is 16 Hz and this is characteristic of vinylic protons which are trans to each other. The correct answer is compound 3. OH COOH HM HM Cl HX HA HA Cl HX HX Cl HA 2,7-dichloronaphthalene December 2007 – last updated April 2013 39 HM Cl HX HM HA 2,6-dichloronaphthalene Please Keep Absolutely Confidential ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Notes and Errata 1 The H NMR spectra in Problem 147 and in Problem 148 have been referenced incorrectly. Spectra in the book are shifted by 0.6 to 0.8 ppm to higher field than they should be. Problem 147 has correct resonances at approximately δ 2.7 and δ 1.5 with a broad resonance at δ 1.4 ppm. Problem 148 has correct resonances at approximately δ 2.8, δ 1.6 and δ 1.5 with a broad resonance at δ 2.0 ppm. Problem 215 the molecular formula should be C10H9NO4Br2 instead of C8H9NO4Br2. (Corrected 21.4.13) Revision History The answer to problem 296 had the C13 shifts for C3 and C4 interchanged. Corrected 25.8.11. December 2007 – last updated April 2013 40 Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited