Package Title: Solomons Test BankCourse Title: Solomons 11e Chapter Number: 15 Question Type: Multiple Choice 1) Which of these is the rate-determining step in the nitration of benzene? a) Protonation of nitric acid by sulfuric acid b) Protonation of sulfuric acid by nitric acid c) Loss of a water molecule by the protonated species to produce the nitronium ion d) Addition of the nitronium to benzene to produce the arenium ion e) Loss of a proton by the arenium ion to form nitrobenzene Answer: D Topic: Mechanisms and Intermediates Section: 15.2 Difficulty Level: Medium 2) Which of these is the rate-determining step in the sulfonation of benzene? a) Formation of SO3 from sulfuric acid b) Protonation of SO3 sulfuric acid c) Addition of SO3H+ to benzene to form the arenium ion d) Loss of a proton from the arenium ion to form benzenesulfonic acid e) None of these choices. Answer: C Topic: Mechanisms and Intermediates Section: 15.2 Difficulty Level: Medium 3) Which of these is the rate-determining step in the bromination of benzene? a) Complexation of bromine with the iron(III) bromide catalyst b) Formation of Br+ ion c) Addition of Br+ to benzene to form the arenium ion d) Loss of a proton from the arenium ion to form bromobenzene e) None of these choices. 1 Answer: C Topic: Mechanisms and Intermediates Section: 15.2 Difficulty Level: Medium 4) Which of the following structures contribute(s) to the resonance hybrid of the intermediate formed when bromobenzene undergoes para-chlorination? .. .. .. .. : Br : : Br + : Br : : Br : + + + H Cl H Cl H Cl H Cl I II III IV a) I b) II c) III d) IV e) All of these choices. Answer: E Topic: Mechanisms and Intermediates Section: 15.11 Difficulty Level: Medium 5) Which of the following structures contribute(s) to the resonance hybrid of the intermediate formed when chlorobenzene undergoes para-chlorination? .. .. .. .. : Cl : : Cl + : Cl : : Cl : + + + H Cl H Cl H Cl H Cl I II III IV a) I b) II c) III d) IV e) All of these choices. Answer: E Topic: Mechanisms and Intermediates 2 Section: 15.11 Difficulty Level: Medium 6) Which of the following structures contribute(s) to the resonance hybrid of the intermediate formed when acetanilide undergoes para-bromination? +NCOCH :NHCOCH3 : NHCOCH3 : NHCOCH3 3 + + + H Br H Br H Br H Br I II III IV a) I b) II c) III d) IV e) All of these choices. Answer: E Topic: Mechanisms and Intermediates Section: 15.11 Difficulty Level: Medium 7) Which of the following contributors to the resonance stabilized hybrid formed when aniline undergoes para-chlorination would be exceptionally stable? +NH2 : NH2 : NH2 : NH2 + + + H Cl H Cl H Cl H Cl I II III IV a) I b) II c) III d) IV e) None of these choices. Answer: B Topic: Mechanisms and Intermediates Section: 15.11 Difficulty Level: Medium 3 .11 Difficulty Level: Medium 9) Which of the following structures does not contribute to the resonance hybrid of the intermediate formed when nitrobenzene undergoes meta-chlorination? .8) Consider the structures given below. Which of them would be a relatively stable contributor to the hybrid formed when toluene undergoes para bromination? a) I b) II c) III d) IV e) V Answer: C Topic: Mechanisms and Intermediates Section: 15.. :O : O: : O : O: : O : O: N N + H Cl I + N +H H Cl II Cl III a) I b) II c) III d) None of these contribute. Answer: E Topic: Mechanisms and Intermediates Section: 15. e) All of these contribute.. .. . . ..11 Difficulty Level: Medium 10) Consider the resonance forms shown for the arenium ionformed from the bromination of acetanilide. .. Which resonance form contributes most to the overall resonance hybrid? 4 . Answer: D 5 . Answer: C Topic: Mechanisms and Intermediates Section: 15.11 Difficulty Level: Medium 11) Consider the resonance forms shown for the arenium ionformed from the bromination of acetanilide.H I Br O HN HN HN Br O O O H II Br HN H H Br IV III a) I b) II c) III d) IV e) All contribute equally. Which resonance form contributes most to the overall resonance hybrid? a) I b) II c) III d) IV e) All contribute equally. c) lewis acid. the attacking species (the electrophile) necessarily is a: a) neutral species. e) ultraviolet light. Answer: A 6 . c) a Lewis acid. b) a Lewis base. d) proton.Topic: Mechanisms and Intermediates Section: 15. in addition to the halogen: a) a hydroxide ion.11 Difficulty Level: Medium 12) The electrophilic bromination or chlorination of benzene requires. e) carbocation. d) peroxide.2 Difficulty Level: Medium 14) Which of these liquids would be unsuitable as an inert solvent for a Friedel-Crafts reaction? a) Chlorobenzene b) Nitrobenzene c) Acetophenone d) (Trifluoromethyl) benzene e) All of these choices could be used.3 Difficulty Level: Easy 13) In electrophilic aromatic substitution. Answer: C Topic: Other EAS Considerations Section: 15. Answer: C Topic: Other EAS Considerations Section: 15. b) positively charged species. a) -OCH2CH3 b) -NO2 c) -F d) -CF3 e) -NHCOCH3 Answer: C Topic: Other EAS Considerations Section: 15. a) Benzene b) Chlorobenzene c) Nitrobenzene d) Toluene e) tert-Butylbenzene Answer: C 7 .11 Difficulty Level: Medium 17) This molecule does not normally participate as a reactant in a Friedel-Crafts reaction.8 Difficulty Level: Medium 16) This substituent deactivates the benzene ring towards electrophilic substitution but directs the incoming group chiefly to the ortho and para positions.8 Difficulty Level: Medium 15) Undesired polysubstitution of an aromatic nucleus is most likely to be encountered in the case of: a) Friedel-Crafts alkylation b) Friedel-Crafts acylation c) Nitration d) Sulfonation e) Chlorination Answer: A Topic: Other EAS Considerations Section: 15.10 and 15.Topic: Other EAS Considerations Section: 15. 8 Difficulty Level: Medium 20) Which reagent would you use as the basis for a simple chemical test that would distinguish between toluene and vinylbenzene (C6H5CH=CH2)? a) NaOH/H2O b) Br2/CCl4 c) NaBH4 d) HCl/H2O e) NaI in acetone Answer: B 8 .8 Difficulty Level: Medium 18) Which one of these molecules can be a reactant in a Friedel-Crafts reaction? a) Aniline b) Nitrobenzene c) Chloroethene d) Bromobenzene e) p-Bromonitrobenzene Answer: D Topic: Other EAS Considerations Section: 15.Topic: Other EAS Considerations Section: 15.8 Difficulty Level: Medium 19) Which one of these molecules can be a reactant in a Friedel-Crafts reaction? a) Aniline b) Benzenesulfonic acid c) Chloroethene d) Bromobenzene e) p-Bromonitrobenzene Answer: D Topic: Other EAS Considerations Section: 15. Topic: Functional Group Tests Sections: 14.2. H2SO4 Answer: C Topic: Nomenclature.2-diphenylbutane Answer: B Topic: Nomenclature.3 and 15. Reaction Products Section: 14.11 and 15. 14.3 Difficulty Level: Medium 21) Which reagent or test could you use to distinguish between phenylacetylene and vinylbenzene? a) NaOH/H2O b) Br2/CCl4 c) IR Spectroscopy d) CrO3/H2SO4 e) Concd. Functional Group Tests Section: 14.2 and 15. 14.3 Difficulty Level: Medium 22) What is the chief product of the Friedel-Crafts alkylation of benzene with 1-butene and HF? a) butylbenzene b) 2-phenylbutane c) 2-methyl-1-phenylpropane d) t-butylbenzene e) 2.6 Difficulty Level: Hard 23) What is the chief product of the Friedel-Crafts alkylation of benzene with 1-butene and AlCl3? a) butylbenzene b) 2-phenylbutane c) 2-methyl-1-phenylpropane d) t-butylbenzene e) 2.2.2-diphenylbutane 9 . Reaction Products Section: 14. Reaction Products Section: 14.8 Difficulty Level: Hard 25) A mixture of chlorobenzene (1 mol) and anisole (1mol) is allowed to react with Br2 (0.3. Reaction Products Section: 14. 15.6 Difficulty Level: Hard 24) A mixture of chlorobenzene (1 mol) and acetanilide (1mol) is allowed to react with Br2 (0.Answer: B Topic: Nomenclature. What is the principal product of the competing reactions? a) 1-bromo-4-chlorobenzene b) 1-bromo-2-chlorobenzene c) 1-bromo-3-chlorobenzene d) 4-bromoanisole e) 3-bromoanisole Answer: D Topic: Nomenclature.2.3.5 mol) in the presence of trace amounts of FeBr3.2 and 15.8 Difficulty Level: Hard 26) Which of the following reactions could be used to synthesize tert-butylbenzene? a) C6H6 + CH2=C(CH3)2 H2SO4 10 .5 mol) in the presence of trace amounts of FeBr3. and 15. and 15. What is the principal product of the competing reactions? a) 1-bromo-4-chlorobenzene b) 1-bromo-2-chlorobenzene c) 1-bromo-3-chlorobenzene d) 4-bromoacetanilide e) 3-bromoacetanilide Answer: D Topic: Nomenclature.2. 15. H2SO4 AlCl3 Answer: D Topic: Synthesis Section: 15. AlCl3 Answer: D Topic: Synthesis 11 . e) None of these choices. e) None of these choices.b) C6H6 + (CH3)3COH c) C6H6 + (CH3)3CCl d) All of these choices.6 Difficulty Level: Easy 28) Which of the following reactions could be used to synthesize tert-butylbenzene? a) b) c) C6H6 + (CH3)3CCl d) All of these choices.6 Difficulty Level: Easy 27) Which of the following reactions could be used to synthesize tert-butylbenzene? a) C6H6 + CH2=C(CH3)2 H2SO4 b) c) C6H6 + (CH3)3CCl d) All of these choices. AlCl3 Answer: D Topic: Synthesis Section: 15. e) None of these choices. 6 Difficulty Level: Easy 29) Consider the following reaction: what is the expected product? NH2 Br2.Section: 15.3 Difficulty Level: Easy 30) Which of the following reactions would yield isopropylbenzene as the major product? CH3CHCH3 Benzene b) OH H2SO4 CH3CHCH3 Benzene c) Cl AlCl3 12 . H2O ? Cl Cl NH2 Br Br H2 N Cl Br Br Cl NH2 II I Br Br III NH2 NH2 Br Br Br Cl Cl IV V a) I b) II c) III d) IV e) V Answer: B Topic: Synthesis Section: 15. Benzene CH3CH2CH2Cl AlCl3 d) e) All of these choices. Answer: E Topic: Synthesis Section: 15.6 Difficulty Level: Medium 32) Which of the following reactions would yield isopropylbenzene as the major product? a) 13 .6 Difficulty Level: Medium 31) Which of the following reactions would yield isopropylbenzene as the major product? a) CH3CHCH3 Benzene b) OH H2SO4 CH3CHCH3 Benzene c) Cl AlCl3 CH3CH2CH2Cl Benzene AlCl3 d) e) All of these choices. Answer: E Topic: Synthesis Section: 15. Answer: E Topic: Synthesis Section: 15.6 Difficulty Level: Medium 34) Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane? 14 .b) CH3CHCH3 Benzene c) Benzene Cl AlCl3 CH3CH2CH2Cl AlCl3 d) e) All of these choices. Answer: E Topic: Synthesis Section: 15.6 Difficulty Level: Medium 33) Which of the following reactions would produce isopropylbenzene? Cl Benzene a) Benzene b) AlCl3 HF OH Benzene H2SO4 c) Br Benzene AlCl3 d) e) All of these choices. Answer: E 15 . AlCl3 ⎯⎯→ Answer: C Topic: Synthesis Sections: 11.9 and 15. Fe ⎯⎯→ b) C6H5CH2CH3 + Cl2. Fe ⎯⎯→ b) C6H5CH2CH3 + Cl2. 400°C ⎯⎯→ c) C6H5CH2CH2OH + SOCl2 ⎯⎯→ d) C6H5CH=CH2 + HCl.6 Difficulty Level: Medium 35) Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane? a) C6H5CH2CH3 + Cl2. 400°C ⎯⎯→ c) C6H5CH2CH2OH + PCl5 ⎯⎯→ d) C6H5CH=CH2 + HCl. peroxide ⎯⎯→ e) C6H6 + CH3CH2Cl.9 and 15.a) C6H5CH2CH3 + Cl2.6 Difficulty Level: Medium 36) Which of the following reactions would produce cumene? Cl Benzene a) Benzene b) AlCl3 HF OH Benzene H2SO4 c) Br Benzene AlCl3 d) e) All of these choices. AlCl3 ⎯⎯→ Answer: C Topic: Synthesis Sections: 11. peroxide ⎯⎯→ e) C6H6 + CH3CH2Cl. Answer: E Topic: Synthesis Section: 15. in greater than 50% yield)? NH2 NH2 + CH3Cl I AlCl3 NH2 and CH3 CH3 NH2 II NH2 + CH3Cl AlCl3 CH3 III + CH3CH2CH2Cl CH2CH2CH3 AlCl3 16 ..Topic: Synthesis Section: 15.e.6 Difficulty Level: Hard 37) Which of the following reactions would yield cumene as the major product? Benzene a) CH3CH CH2 H2SO4 CH3CHCH3 Benzene b) OH H2SO4 CH3CHCH3 Benzene c) Benzene Cl AlCl3 CH3CH2CH2Cl AlCl3 d) e) All of these choices.6 Difficulty Level: Hard 38) Which of the following reactions would give the product(s) indicated in substantial amounts (i. 6 and 15.8 Difficulty Level: Medium 40) What would you expect to be the major product obtained from the following reaction? 17 .a) I b) II c) III d) All of these choices. Answer: E Topic: Reaction Products Section: 15.6 and 15.8 Difficulty Level: Easy 39) What would you expect to be the major product obtained from the following reaction? O excess HN AlCl3 ? CH3Cl O O O HN HN HN I II III O O HN HN IV V a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15. e) None of these choices. 7 and 15.O2N O AlCl3 + O2 N O I II O2N O O2N O2N O ? Cl III O2 N IV V O O a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 15. 18 .8 Difficulty Level: Medium 41) The major product(s) of the following reaction. p. m.to the nitro group.O O AlCl3 + ? Cl O O O O O O I O II III O IV O V O would be: a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.to the methylene group. Answer: A Topic: Reaction Products 19 .8 Difficulty Level: Medium 42) What might be predicted to happen when the following substance undergoes Friedel-Crafts acylation? O2N CH2 A B a) Substitution occurs in ring B. c) Substitution occurs in ring A. e) None of these choices.to the methylene group. No reaction will occur. o. o.to the methylene group.7 and 15. b) Substitution occurs in ring A. d) Substitution occurs in ring B. 8 Difficulty Level: Medium 43) What would be the product of the following reaction sequence? OH i) SOCl2 ? ii) C6H6.9 Difficulty Level: Medium 44) What would be the product of the following reaction sequence? 20 . HCl.Section: 15.7 and 15. heat O O OH OH II I IV III V a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.7 and 15. AlCl3 O iii) Zn(Hg). OH i) SOCl 2 ii) C6H6. HCl. AlCl3 iii) Zn(Hg). AlCl3 iii) H2NNH2/KOH O ? O O OH OH II I III V IV a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.7 and 15.9 Difficulty Level: Medium 45) What would be the product of the following reaction sequence? OH O i) PCl5 ii) C6H6. heat O ? OH O OH I II IV III V a) I 21 . 7 and 15.b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.9 Difficulty Level: Medium 47) What would be the product of the following reaction sequence? 22 .7 and 15.9 Difficulty Level: Medium 46) What would be the product of the following reaction sequence? a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15. HCl. heat ? O OH II I III O OH IV V a) I b) II c) III d) IV e) V Answer: B Topic: Reaction Products Section: 15.9 Difficulty Level: Medium 48) What would be the product of the following reaction sequence? 23 . AlCl3 iii) Zn(Hg).7 and 15.OH O i) SOCl2 ii) C6H6. 9 Difficulty Level: Medium 49) Which would be the product of the following reaction sequence? O i) SOCl2 ? OH ii) benzene.a) I b) II c) III d) IV e) V Answer: B Topic: Reaction Products Section: 15. AlCl3 iii) Zn(Hg).7 and 15. HCl SO2 CO2 CH2 I II III O IV V 24 . 9 Difficulty Level: Medium 50) Which would be the product of the following reaction sequence? a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.7 and 15.9 Difficulty Level: Medium 51) Which would be the product of the following reaction sequence? 25 .7 and 15.a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15. 9 Difficulty Level: Medium 52) Which would be the product of the following reaction sequence? a) I b) II c) III d) IV 26 . HCl ? SO2 CO2 CH2 I II III O IV V a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.O OH i) PCl5 ii) benzene.7 and 15. AlCl3 iii) Zn(Hg). 7 and 15. X. of the following reaction sequence? 27 .9 Difficulty Level: Medium 54) Which would be the product.7 and 15. X. of the following reaction sequence? O O Ph O Ph i) benzene. HCl X OH + O SO2 CO2 CH2 I II III O IV V a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.e) V Answer: C Topic: Reaction Products Section: 15.9 Difficulty Level: Medium 53) Which would be the product. AlCl3 ii) Zn(Hg). 9 Difficulty Level: Medium 55) The major product(s). of the following reaction. D. 28 .a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.7 and 15. D. Answer: D Topic: Reaction Products Section: 15. 29 .3 and 15. of the following reaction.O C CH2 Br Br2 D FeBr3 O O C CH2 C CH2 Br I II O O C CH2 C CH2 Br Br III IV would be: a) I b) II c) III d) IV e) Approximately equal amounts of I and II.10 Difficulty Level: Medium 56) The major product. O H2SO4 D SO3 O O HO3S II I SO3H SO3H O O SO3H IV III O SO3H V would be: a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 15.10 Difficulty Level: Medium 57) What would you expect to be the major product obtained from the following reaction? 30 .3 and 15. 10 Difficulty Level: Medium 58) What would you expect to be the major product obtained from the following reaction? NO2 Br2 NO2 ? FeBr3 SO3H NO2 NO2 NO2 Br Br SO3H SO3H Br SO3H SO3H Br I II III IV a) I b) II c) III d) IV e) Equal amounts of II and IV. Answer: C Topic: Reaction Products Section: 15.COOH SO3H COOH Br Br2 ? FeBr3 COOH COOH COOH Br SO3H SO3H Br SO3H SO3H Br I II III IV a) I b) II c) III d) IV e) Equal amounts of II and IV.3 and 15.3 and 15. Answer: C Topic: Reaction Products Section: 15.10 31 . FeBr3 ? O O O O Br O O O Br Br II I III Br O O O Br O IV V a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 15.Difficulty Level: Medium 59) What would you expect to be the major product obtained from the following reaction? O Br2.10 Difficulty Level: Medium 60) What would you expect to be the major product obtained from the following reaction? 32 .3 and 15. Br2 FeBr3 ? Br Br II I Br III Br Br IV V a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.3 and 15.10 Difficulty Level: Medium 61) What would you expect to be the major product obtained from the following reaction? 33 .1 equiv. 10 Difficulty Level: Medium 62) What would you expect to be the major product obtained from the following reaction? O Cl2. FeCl3 ? HN Cl O O O HN HN II III Cl HN Cl I O O HN HN Cl Cl IV V 34 .1 equiv. Cl2 FeCl3 ? Cl Cl Cl II I III Cl Cl IV V a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.3 and 15. 10 Difficulty Level: Medium 35 Br .3 and 15.10 Difficulty Level: Medium 63) What would you expect to be the major product obtained from the following reaction? 1 equivalent Br2 O ? FeBr3 Br O O O Br I III II Br O O Br IV V a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.3 and 15.a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15. 3 and 15.64) What would you expect to be the major product obtained from the monobromination of mdichlorobenzene? Cl Cl Cl Br Cl Cl Br Br I II Cl III a) I b) II c) III d) Equal amounts of I and II. e) Equal amounts of I. Answer: A Topic: Reaction Products Section: 15.3 and 15.10 Difficulty Level: Medium 65) Which would be the major product(s) of the following reaction? H3CO O Br2. e) I and III in roughly equal amounts. II and III.10 Difficulty Level: Medium 36 . Answer: B Topic: Reaction Products Section: 15. FeBr3 H3CO H3CO O O ? H3CO O Br Br I Br2Fe II III a) I b) II c) III d) I and II in roughly equal amounts. 66) What would you expect to be the major product obtained from the following reaction? O HNO3 H2SO4.4 and 15.10 Difficulty Level: Medium 67) What would you expect to be the major product obtained from the following reaction? 37 . heat HN O O2N HN ? O NO2 O HN HN II III O2N I O O HN HN IV NO2 NO2 V a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15. O HNO3 H2SO4, heat O O ? O O O 2N O O O O2 N II I III NO2 O O O O NO2 IV V a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.4 and 15.10 Difficulty Level: Medium 68) What would be the major product(s) of the following reaction? CO2H HNO3 H2SO4, heat NO2 CO2H NO2 NO2 I CO2H NO2 NO2 II CO2H O2N ? O2N CO2H NO2 NO2 IV III a) I b) II c) III 38 NO2 d) IV e) Approximately equal amounts of II and IV. Answer: C Topic: Reaction Products Section: 15.4 and 15.10 Difficulty Level: Medium 69) What would you expect to be the major product obtained from the following reaction? 1 equiv. HNO3 H2SO4, heat ? O 2N NO2 II I NO2 III NO2 O2N IV V a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.4 and 15.10 Difficulty Level: Medium 70) What would you expect to be the major product obtained from the following reaction? 39 HNO3 H2SO4, heat HN ? O2N HN HN HN NO2 O2N II I III NO2 HN HN NO2 IV V a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 15.4 and 15.10 Difficulty Level: Medium 71) What would you expect to be the major product(s) obtained from the mononitration of mdichlorobenzene? Cl Cl Cl NO2 Cl I Cl NO2 O2N II Cl III a) I b) II c) III d) Equal amounts of I and II. e) Equal amounts of I, II and III. Answer: B 40 4 and 15. of the following reaction 41 . Answer: C Topic: Reaction Products Section: 15. D. heat SO3H HO HO O O HO HO O NO2 SO3H I ? O O2N SO3H O2N NO2 II SO3H SO3H IV III a) I b) II c) III d) IV e) Equal amounts of I and II.10 Difficulty Level: Medium 72) What would you expect to be the major product(s) obtained from the following reaction? HO O HNO3 H2SO4 .4 and 15.Topic: Reaction Products Section: 15.10 Difficulty Level: Medium 73) The major product(s). 4 and 15.HNO3 O D H2SO4 O O2N O I NO2 O II NO2 O NO2 IV III would be: a) I b) II c) III d) IV e) Equal amounts of I and II. Answer: D Topic: Reaction Products Section: 15. 42 .10 Difficulty Level: Medium 74) Which would be the major product(s) of the following reaction? HO O HNO3 H2SO4 HO HO O O ? HO O NO2 NO2 I HO3S II III a) I b) II c) III d) I and II in roughly equal amounts. e) I and III in roughly equal amounts.10 Difficulty Level: Medium 75) Which would be the major product(s) of the following reaction? H3CO O HNO3 H2SO4 H3CO H3CO O O ? H3CO O NO2 NO2 I HO3S II III a) I b) II c) III d) I and II in roughly equal amounts.4 and 15.10 Difficulty Level: Medium 76) What would be the major product(s) of the following reaction? 43 .4 and 15. Answer: A Topic: Reaction Products Section: 15. Answer: A Topic: Reaction Products Section: 15. e) I and III in roughly equal amounts. 5 and 15. Answer: C 44 . Answer: C Topic: Reaction Products Section: 15. e) Equal amounts of II and IV.10 Difficulty Level: Medium 77) What would be the major product(s) of the following reaction? O H2SO4 NO2 ? SO3 O O O O HO3S SO3H NO2 I NO2 SO3H II HO3S NO2 NO2 IV III a) I b) II c) III d) Equal amounts of I and IV. e) Equal amounts of II and IV.O H2SO4 ? NO2 O O O O HO3S SO3H NO2 I NO2 SO3H HO3S II NO2 NO2 IV III a) I b) II c) III d) Equal amounts of I and IV. 10 Difficulty Level: Medium 79) The major product(s). hν CH3CH2 CH3CH2 A 400 . Cl2. e) Approximately equal amounts of I and III.10 Difficulty Level: Medium 78) The major product(s). Cl Cl Cl SO3 H2SO4 C Cl Cl SO3H Cl Cl SO3H I HO3S II Cl III would be: a) I b) II c) III d) Approximately equal amounts of I and II. C. of the following reaction.Topic: Reaction Products Section: 15. Answer: B Topic: Reaction Products Section: 15. of the following reaction. A.600 oC Cl CH3CH2 ClCH2CH2 CH3CH Cl Cl I II III IV would be: 45 .5 and 15.5 and 15. d) III e) IV Answer: A Topic: Reaction Products Section: 15. d) III e) IV Answer: E Topic: Reaction Products Section: 15.a) I b) II c) A mixture of I and II.600oC Cl Cl Cl Cl Cl Cl Cl Cl I II IV III a) I b) II c) A mixture of I and II. 46 .12 Difficulty Level: Medium 81) The major product(s) of the following reaction. excess Cl2 ? 400o .12 Difficulty Level: Medium 80) The major product(s) of the following reaction. 12 Difficulty Level: Medium 82) The major product(s). 47 IV .excess NBS ? ROOR Br Br Br Br Br Br Br Br I II IV III a) I b) II c) A mixture of I and II. of the following reaction. NBS ? ROOR Br Br Br Br I II III would be: a) I b) II c) A mixture of I and II. A. d) III e) IV Answer: D Topic: Reaction Products Section: 15. d) III e) IV Answer: E Topic: Reaction Products Section: 15.12 Difficulty Level: Medium 83) What would be the major product of the following reaction? Cl2 CH2CH2CH3 Cl CH2CH2CH3 ? 400 oC CH2CH2CH3 CHCH2CH3 Cl Cl I II CH2CHCH3 III CH2CH2CH2Cl Cl IV V a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.12 Difficulty Level: Medium 84) What would be the major product of the following reaction? 48 . 12 Difficulty Level: Medium 85) What would be the major product of the following reaction? excess NBS ? ROOR Br Br Br Br Br Br Br Br I III II Br IV Br IV 49 .NBS ? ROOR Br Br Br I Br Br III II V IV a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 15. a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.12 Difficulty Level: Medium 87) What would you expect to be the major product obtained from the following reaction? 50 .12 Difficulty Level: Medium 86) What would you expect to be the major product obtained from the following reaction? Cl2 ? peroxides Cl Cl II I Cl III Cl Cl IV V a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15. ROOR ? light Br Br Br I II III Br Br IV V a) I b) II 51 .Cl2 ? light Cl Cl Cl II I III Cl Cl IV V a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.12 Difficulty Level: Medium 88) What would be the major product of the following reaction? NBS. and light and 2) Br2. Answer: B Topic: Reaction Products Section: 15. the chief product is: Br CCl3 CCl3 Br CCl3 Br Cl I Br II III IV a) I b) II c) III d) IV e) A mixture of III and IV.c) III d) IV e) V Answer: C Topic: Reaction Products Section: 15.12 Difficulty Level: Medium 89) When toluene is reacted in turn with 1) Cl2 (large excess).3 and 15. heat.12 Difficulty Level: Medium 90) What would you expect to be the major product obtained from the following reaction? 52 .FeBr3. heat N N O2N O O N N N ? NO2 O N N N O 2N II I III O O N N N N NO2 NO2 IV V a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.10 Difficulty Level: Hard 91) What would you expect to be the major product obtained from the following reaction? 53 .4 and 15.O HNO3 H2SO4. N=O Br2 FeBr3 N=O N=O N=O Br Br Br I II III N-OBr Br IV a) I b) II c) III d) IV e) A mixture of II and III.10 Difficulty Level: Hard 92) The reaction of benzene with (CH3)3CCH2Cl in the presence of anhydrous aluminum chloride produces principally which of these? 54 . Answer: E Topic: Reaction Products Section: 15.4 and 15. 8 Difficulty Level: Hard 93) The reaction of benzene with chloride produces principally which of these? Cl in the presence of anhydrous aluminum II I IV III V a) I b) II c) III 55 .II I III IV V a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.6 and 15. 6 and 15.d) IV e) V Answer: D Topic: Reaction Products Section: 15.6 and 15.8 Difficulty Level: Hard 94) The reaction of benzene with chloride produces principally which of these? in the presence of anhydrous aluminum II I IV III V a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 15.8 Difficulty Level: Hard 56 . 8 Difficulty Level: Hard 96) The reaction of benzene with produces principally which of these? in the presence of anhydrous aluminum chloride 57 .Cl 95) The reaction of benzene with produces principally which of these? in the presence of anhydrous aluminum chloride II I IV III V a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 15.6 and 15. heat. H2SO4 (3) Br2.6 and 15.OH-.a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 15.8 Difficulty Level: Hard 97) Toluene is subjected to the action of the following reagents in the order given: (1) KMnO4. FeBr3 What is the final product of this sequence? 58 . then H3O+ (2) HNO3. CO2H Br CO2H CO2H NO2 Br NO2 I NO2 Br II III Br CH3 NO2 Br NO2 CO2H IV V a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 15. then H3O+ (2) HNO3.3. and 15.4.OH-. heat.13 Difficulty Level: Hard 98) Toluene is subjected to the action of the following reagents in the order given: (1) KMnO4. H2SO4 (3) Cl2. 15. 15. FeCl3 What is the final product of this sequence? a) I b) II c) III d) IV 59 .10. 15. i) AlCl3 ii) N-Bromosuccinimide.6. and 15. 15. 15.3. 15.e) V Answer: D Topic: Reaction Products Section: 15. heat iv) m-CPBA v) CH3MgBr vi) NH4Cl Cl + ? Br HO HO II I III HO HO IV V a) I b) II c) III d) IV e) V Answer: D Topic: Reaction products Section: 15.13 Difficulty Level: Hard 99) What product would result from the following series of reactions. peroxides iii) CH3ONa.12. CH3OH. 60 .4.10.13 Difficulty Level: Hard 100) What product would result from the following series of reactions. 6.12. CH3OH. heat iv) m-CPBA v) CH3MgBr vi) NH4Cl + ? Br HO HO II I III HO HO IV V a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 15.13 Difficulty Level: Hard 101) What product would result from the following series of reactions. peroxides iii) CH3ONa. 15.i) HF ii) N-Bromosuccinimide. 15. 61 . 6.i) BF3 ii) N-Bromosuccinimide. 15.13 Difficulty Level: Hard 102) Which of the following is not a meta-directing substituent when present on the benzene ring? a) -NHCOCH3 b) -NO2 c) -N(CH3)3+ d) -C≡N e) -CO2H Answer: A Topic: Directing Effects Section: 15. peroxides iii) CH3ONa.10 Difficulty Level: Easy 62 .12. heat iv) m-CPBA v) CH3MgBr vi) NH4Cl OH + ? Br HO HO II I III HO HO IV V a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 15. 15. CH3OH. Cl COOH Cl NHCOCH3 O CCH3 Cl NO2 OH I II III CH3 CH2CH3 IV V a) I b) II c) III d) IV e) V Answer: C Topic: Directing Effects Section: 15.103) Which of the following is not a meta-directing substituent when present on the benzene ring? a) -N=O b) -NO2 c) -N(CH3)3+ d) -C≡N e) -CO2H Answer: A Topic: Directing Effects Section: 15. In which of these cases does the arrow not indicate the chief position of nitration.14 Difficulty Level: Easy 105) Which of the following compounds would yield the greatest amount of meta product when subjected to ring nitration? 63 .10 Difficulty Level: Easy 104) Each of the five disubstituted benzenes shown below is nitrated. 10 Difficulty Level: Easy 107) Which of the following is not an ortho-para director in electrophilic aromatic substitution? a) -CCl3 b) -OCH3 c) -CH3 d) -F e) -NH2 Answer: A 64 .HO O HO O HO O I O O HO OH II IV III V a) I b) II c) III d) IV e) V Answer: A Topic: Directing Effects Section: 15.10 Difficulty Level: Easy 106) Which of the following is not an ortho-para director in electrophilic aromatic substitution? a) -CF3 b) -OCH3 c) -CH3 d) -F e) -NH2 Answer: A Topic: Directing Effects Section: 15. 10 Difficulty Level: Easy 110) Which is the best prediction of the site(s) of substitution when 3-methylphenol is nitrated? a) C-2 b) C-4 c) C-5 d) C-6 e) C-4 and C-6 Answer: E 65 .Topic: Directing Effects Section: 15.10 Difficulty Level: Easy 109) Which of the following is not an ortho-para director in electrophilic aromatic substitution? a) b) -OCH3 c) -CH3 d) -F e) -NH2 Answer: A Topic: Directing Effects Section: 15.10 Difficulty Level: Easy 108) Which of the following is not an ortho-para director in electrophilic aromatic substitution? a) -SO3H b) -OCH3 c) -CH3 d) -F e) -NH2 Answer: A Topic: Directing Effects Section: 15. Answer: A Topic: Directing Effects Section: 15.10 and 15. d) nitrate slowly in the meta position. will a) nitrate rapidly in the ortho-para positions. b) nitrate slowly in the ortho-para positions. c) One or more halogen atoms are present in the group. e) fail to nitrate under any conditions. d) One or more oxygen atoms are present in the group. C6H5CF3.11 Difficulty Level: Easy 113) Which of these compounds gives essentially a single product on electrophilic substitution of a third group? a) p-chlorotoluene b) m-ethylanisole c) 1-bromo-2-chlorobenzene d) m-xylene e) 3-hydroxybenzoic acid Answer: D 66 . e) The group is attached to the ring through a carbon atom. Answer: D Topic: Directing Effects Section: 15.Topic: Directing Effects Section: 15. c) nitrate rapidly in the meta position.10 Difficulty Level: Easy 112) What feature is common to all meta-directing groups? a) The atom directly attached to the ring has a full or well-developed partial positive charge. b) The atom directly attached to the ring is doubly bonded to oxygen.10 Difficulty Level: Easy 111) (Trifluoromethyl)benzene. Answer: C Topic: Directing Effects Section: 15.11 Difficulty Level: Medium 116) The ortho/para product ratio is expected to be the smallest for the bromination of which of these? a) Toluene b) Isopropylbenzene c) Butylbenzene 67 .10 Difficulty Level: Medium 114) Arrange the following compounds in order of decreasing reactivity in electrophilic substitution: O I O Br II III NO2 IV V a) V > II > I > III > IV b) II > V > III > I > IV c) IV > I > III > V > II d) III > II > I > IV > V e) IV > V > II > I > III Answer: B Topic: Directing Effects Section: 15. d) The atom directly attached to the aromatic ring is more electronegative than carbon.10 Difficulty Level: Medium 115) What is a feature found in all ortho-para directing groups? a) An oxygen atom is directly attached to the aromatic ring. b) The atom attached to the aromatic ring must possess an unshared pair of electrons. c) The group has the ability to delocalize the positive charge of the arenium ion. e) The group contains a multiple bond.Topic: Directing Effects Section: 15. light. peroxides Answer: B Topic: Reagents Section: 15. light.10 and 15.10 Difficulty Level: Medium 118) Which reagent(s) would you use to carry out the following transformation? ethylbenzene ⎯⎯→ 2.10 Difficulty Level: Medium 119) Which reagent(s) would you use to carry out the following transformation? t-butylbenzene ⎯⎯⎯→ p-chloro substitution product a) Cl2.d) sec-Butylbenzene e) tert-Butylbenzene Answer: E Topic: Directing Effects Section: 15. AlCl3 e) HCl. FeCl3 c) SOCl2 d) C2H5Cl. light.3 and 15.15 Difficulty Level: Medium 117) Which reagent(s) would you use to carry out the following transformation? isopropylbenzene ⎯⎯⎯→ 2. FeCl3 c) SOCl2 d) C2H5Cl. and heat 68 . and heat b) Cl2.and 4-chloro-1-ethylbenzene a) Cl2.3 and 15. and heat b) Cl2.and 4-chloro-1-isopropylbenzene a) Cl2. AlCl3 e) None of these choices. Answer: B Topic: Reagents Section: 15. ROOR Answer: C Topic: Reagents Section: 15. FeCl3 c) SOCl2 d) C2H5Cl. light b) PBr3 c) Br2. CCl4. AlCl3 e) HCl. light. or heat b) Cl2.3 and 15.and 4-bromo-1-cyclopentylbenzene from cyclopentylbenzene? a) N-Bromosuccinimide (NBS).b) Cl2.12 Difficulty Level: Medium 121) Which reagent(s) would you use to synthesize 2.10 Difficulty Level: Medium 122) Which reagent would you use to carry out the following transformation? tert-butylbenzene ⎯⎯⎯→ p-tert-butylbenzenesulfonic acid 69 . FeBr3 d) CH3CH2Br. AlCl3 e) HCl. O2 Answer: A Topic: Reagents Section: 15.3 and 15.10 Difficulty Level: Medium 120) Which reagent(s) would you use to carry out the following transformation? ethylbenzene ⎯⎯⎯→ 1-chloro-1-phenylethane a) Cl2. AlBr3 e) HBr. FeCl3 c) SOCl2 d) C2H5Cl. peroxide Answer: B Topic: Reagents Section: 15. + o-tert-butylbenzenesulfonic acid a) HNO3/H2SO4 b) tert-C4H9Cl/AlCl3 c) H2SO3/peroxides d) SO3/H2SO4 e) SO2/H2SO3 Answer: D Topic: Reagents Section: 15.5 and 15.10 Difficulty Level: Medium 123) Which reagent(s) would you use to carry out the following transformation? toluene ⎯⎯⎯→ benzoic acid a) Br2, heat, and light b) Cl2, FeCl3 c) KMnO4, OH-, heat (then H3O+) d) HNO3/H2SO4 e) SO3/H2SO4 Answer: C Topic: Reagents Section: 15.13 Difficulty Level: Medium 124) Which reagent(s) would you use to carry out the following transformation? ethylbenzene ⎯⎯⎯⎯→ benzoic acid a) Cl2, light, and heat b) Cl2, FeCl3 c) KMnO4, OH-, heat (then H3O+) d) HNO3/H2SO4 e) SO3/H2SO4 Answer: C Topic: Reagents Section: 15.13 Difficulty Level: Medium 70 125) Which reagent(s) would you use to carry out the following transformation? cumene ⎯⎯⎯→ 2- and 4-chlorocumene a) Cl2, light, and heat b) Cl2, FeCl3 c) SOCl2 d) C2H5Cl, AlCl3 e) HCl, peroxides Answer: B Topic: Reagents Section: 15.3 and 15.10 Difficulty Level: Hard 126) Which reagent(s) would you use to carry out the following transformation? toluene ⎯⎯⎯→ benzyl bromide a) Br2, FeBr3 b) N-Bromosuccinimide, ROOR, hν c) HBr d) Br2/CCl4 e) NaBr, H2SO4 Answer: B Topic: Reagents Section: 15.12 Difficulty Level: Hard 127) The compound 4-bromo-1-propylbenzene is best made from benzene by the application of these reagents in the order shown: a) (1) Br2,Fe (2) CH3CH2CH2Cl, AlCl3 b) (1) CH3CH2CH2Cl, AlCl3 (2) Br2,Fe 1) CH3CH2CCl , AlCl3 2) Br2, Fe 3) Zn(Hg), HCl c) O 1) CH3CH2CCl , AlCl3 2) Zn(Hg), HCl 3) Br2, Fe O d) e) (1) (CH3)2CHCl, AlCl3 (2) Br2,Fe 71 Answer: D Topic: Reagents Section: 15.14 Difficulty Level: Hard 128) The compound 4-bromo-1-propylbenzene is best made from benzene by the application of these reagents in the order shown: a) (1) Br2,Fe (2) CH3CH2CH2Cl, AlCl3 b) (1) CH3CH2CH2Cl, AlCl3 (2) Br2,Fe 1) CH3CH2CCl , AlCl3 2) Br2, Fe 3) Zn(Hg), HCl O c) d) e) (1) (CH3)2CHCl, AlCl3 (2) Br2,Fe Answer: D Topic: Reagents Section: 15.14 Difficulty Level: Hard 129) Which of the following compounds would be most reactive toward electrophilic substitution? OH CH3 I II Br III a) I b) II c) III d) IV e) V Answer: A Topic: Relative Reactivities Section: 15.11 Difficulty Level: Easy 72 CHO NO2 IV V 130) Which of the following compounds would be least reactive toward electrophilic substitution? OH CH3 I II Br III CHO NO2 IV V a) I b) II c) III d) IV e) V Answer: E Topic: Relative Reactivities Section: 15.11 Difficulty Level: Easy 132) Which of the following compounds would be least reactive toward electrophilic substitution? 73 .11 Difficulty Level: Easy 131) Which of the following compounds would be most reactive to ring bromination? CH3 NO2 I II CF3 III Cl NH2 IV V a) I b) II c) III d) IV e) V Answer: E Topic: Relative Reactivities Section: 15. 11 Difficulty Level: Easy 134) Which of the following compounds would be most reactive toward ring nitration? 74 .O O NO2 NH NO2 I II IV III V a) I b) II c) III d) IV e) V Answer: B Topic: Relative Reactivities Section: 15.11 Difficulty Level: Easy 133) Which of the following compounds would be most reactive toward electrophilic substitution? O O NO2 NH NH2 NO2 I II IV III V a) I b) II c) III d) IV e) V Answer: E Topic: Relative Reactivities Section: 15. 11 Difficulty Level: Easy 136) Which of the following compounds would be most reactive toward ring bromination? 75 .11 Difficulty Level: Easy 135) Which of the compounds listed below would you expect to give the greatest amount of meta-product when subjected to ring bromination? OH I HO O II NH2 III OCH3 CH3 IV V a) I b) II c) III d) IV e) V Answer: B Topic: Relative Reactivities Section: 15.O O O I a) I b) II c) III d) IV e) V II CF3 III OH NH IV V Answer: D Topic: Relative Reactivities Section: 15. O O HO O NH2 OCH3 O O O II I IV III V a) I b) II c) III d) IV e) V Answer: C Topic: Relative Reactivities Section: 15.11 Difficulty Level: Easy 137) Which of the compounds listed below would you expect to give the greatest amount of meta-product when subjected to ring nitration? O I II O NH III OCH3 CH3 IV V a) I b) II c) III d) IV e) V Answer: B Topic: Relative Reactivities Section: 15.11 Difficulty Level: Easy 138) Which of the following compounds would you expect to be most reactive toward ring nitration? a) Benzene b) Toluene 76 . 12 77 IV .11 Difficulty Level: Medium 139) Which of the following compounds would you expect to be most reactive toward ring nitration? a) Benzene b) Toluene c) m-Xylene d) o-Xylene e) Benzoic acid Answer: C Topic: Relative Reactivities Section: 15.)Which of the following structures would not be a contributor to the resonance hybrid of the benzyl cation? CH3 H H + I CH3 +CH2 CH2 + CH3 + + II III IV a) I b) II c) III d) IV e) V Answer: A Topic: Non-EAS Relative Rates and Intermediates Section: 15.11 Difficulty Level: Medium 140.c) m-Xylene d) p-Xylene e) Benzoic acid Answer: C Topic: Relative Reactivities Section: 15. Difficulty Level: Medium 141) Which of the following carbocations would be most stable? CH3 a) C6H5CH2CH2CHCH2 CH2 b) C6H5CH2CH2CHCH3 CH3 C6H5CH2CH2CCH3 c) CH3 d) C6H5CH2CHCHCH3 CH3 e) C6H5CHCH2CHCH3 Answer: E Topic: Non-EAS Relative Rates and Intermediates Section: 15.12 Difficulty Level: Medium 142) Which alkyl halide would be most reactive in an SN2 reaction? a) C6H5CH2CH2CH2Br C6H5CHCH2Br b) CH3 C6H5CH2CHCH3 Br c) CH3 C6H5CCH2Br d) CH3 Br C6H5CCH3 e) CH3 78 . 15 Difficulty Level: Medium 143) Which alkyl halide would be most reactive in an SN1 reaction? a) C6H5CH2CH2CH2Br C6H5CH2CHCH3 Br CH3 b) C6H5CH2CBr CH3 c) Br C6H5CCH3 d) CH3 CH3 C6H5CCH2Br e) CH3 Answer: D Topic: Non-EAS Relative Rates and Intermediates Section: 15.15 Difficulty Level: Medium 144) The rate of solvolysis in ethanol is least for which of these compounds? a) C6H5CH2Cl C6H5C(CH3)2 Cl b) c) (C6H5)2CHCl C6H5CHCl CH3 d) e) (C6H5)3CCl Answer: A 79 .Answer: A Topic: Non-EAS Relative Rates and Intermediates Section: 15. 15 Difficulty Level: Medium 145) Which of these species is/are proposed as intermediate(s) in the mechanism for the Birch reduction? a) Radical b) Carbanion c) Radical anion d) Two of these choices. 80 .Topic: Non-EAS Relative Rates and Intermediates Section: 15.13 Difficulty Level: Easy 147) Benzoic acid can be prepared by the oxidation of which of the following compounds: a) C6H5CH=CH2 b) C6H5C≡CH c) C6H5COCH3 d) C6H5CH2CH2CH3 e) All of these choices.16 Difficulty Level: Hard 146) Benzoic acid can be prepared by the oxidation of all of the following compounds except this one: a) C6H5CH=CH2 b) C6H5C≡CH c) C6H5COCH3 d) C6H5CH2CH2CH3 e) C6H5C(CH3)3 Answer: E Topic: Synthesis Section: 15. Answer: E Topic: Non-EAS Relative Rates and Intermediates Section: 15. e) All of these choices. 13 Difficulty Level: Easy 149) Which of these is a satisfactory synthesis of 1-bromo-2-phenylethane? a) C6H5CH2CH3 + Br2. then H3O+ b) H3O+. ROOR ⎯⎯→ Answer: D Topic: Synthesis Section: 15. Fe3+ ⎯⎯→ b) C6H5CH2CH3 + Br2. then CO2.13 Difficulty Level: Easy 148) Benzoic acid can be prepared by the oxidation of which of the following compounds: a) C6H5CH=CH2 b) C6H5C≡CH c) C6H5COCH3 d) C6H5CH(CH3)2 e) All of these choices. Answer: E Topic: Synthesis Section: 15.13 Difficulty Level: Medium 150) What reagent can effect the following transformation? Br CO2H Br ? Br CO2H Br CO2H a) CO2.Answer: E Topic: Synthesis Section: 15. 400°C ⎯⎯→ c) C6H5CH2CH2OH + Br2. ROOR ⎯⎯→ e) C6H5CH2CH3 + NBS. CCl4 ⎯⎯→ d) C6H5CH=CH2 + HBr. then H3O+ 81 . heat c) Mg. heat e) KMnO4. KMnO4. OH-. NaOH.13 Difficulty Level: Medium 151) A good synthesis of O (CH3)3C CCH3 would be: O Benzene a) CH3CCl (CH3)3CCl AlCl3 AlCl3 O Benzene b) (CH3)3CCl CH3CCl AlCl3 AlCl3 O Benzene CH3CCl (CH3)2C CH2 AlCl3 HF c) d) More than one of these choices. e) None of these choices.14 Difficulty Level: Medium 152) Which would be a good synthesis of m-nitrobenzoic acid? Benzene a) HNO3/H2SO4 CH3Cl 1. then H3O+ Answer: E Topic: Synthesis Section: 15. heat. heat heat AlCl3 2.d) H2O2. H3O+ 82 . Answer: B Topic: Synthesis Section: 15. c) Answer: C Topic: Nomenclature. heat Answer: C Topic: Synthesis Section: 15. NaOH. followed by H3O+. heat HNO3/H2SO4 2. followed by H3O+. c) CH3Cl/AlCl3. then HNO3/H2SO4. Synthesis Section: 15. then HNO3/H2SO4.4-dimethyl-2-nitrobenzene? Benzene a) Toluene b) p-Xylene HNO3 H2SO4 HNO3 product 2 CH3Cl 2 AlCl3 product H2SO4 HNO3 CH3Cl AlCl3 H2SO4 CH3Cl m-Nitrotoluene AlCl3 d) e) All of these choices are equally good. heat HNO3/H2SO4 2. followed by H3O+. KMnO4. H3O+ heat 1. then separation of isomers. the best method for preparing p-nitrobenzoic acid is: a) HNO3/H2SO4.14 Difficulty Level: Hard 154) Starting with benzene. 83 .Toluene b) Toluene 1. then KMnO4/ OH/heat. H3O+ c) d) More than one of these choices. NaOH. then KMnO4/ OH/heat. b) CH3Cl/AlCl3. then KMnO4/-OH/heat.14 Difficulty Level: Medium 153) Which of the following would be the best synthesis of 1. KMnO4. then CH3Cl/AlCl3. e) None of these choices. then separation of isomers. then KMnO4/-OH/heat. followed by H3O+. Answer: C Topic: Synthesis Section: 15. c) CH3Cl/AlCl3. then CH3Cl/AlCl3. then separation of isomers. then KMnO4/-OH/heat. Answer: B Topic: Synthesis Section: 15. followed by H3O+. then HNO3/H2SO4. then KMnO4/ OH/heat. followed by H3O+. followed by H3O+. then CH3Cl/AlCl3. then separation of isomers. b) CH3Cl/AlCl3. then CO2.14 Difficulty Level: Hard 155) Starting with benzene. followed by H3O+. the best method for preparing m-nitrobenzoic acid is: a) HNO3/H2SO4. e) HNO3/H2SO4. e) HNO3/H2SO4. followed by H3O+. then CO2. then KMnO4/ OH/heat.d) HNO3/H2SO4. then CH3Cl/AlCl3. followed by H3O+. then KMnO4/-OH/heat. then HNO3/H2SO4. d) HNO3/H2SO4.14 Difficulty Level: Hard 156) How might the following synthesis be carried out: CH2CH3 Benzene C 6 H6 a) C 6 H6 b) several ? steps CH3CH2Cl AlCl3 Cl2 FeCl3 Cl Cl2 FeCl3 CH3CH2Cl AlCl3 product product O C6H6 c) CH3CCl Cl2 Zn(Hg) AlCl3 FeCl3 HCl CH3CCl Zn(Hg) Cl2 AlCl3 HCl FeCl3 product O C6H6 d) 84 product . e) None of these syntheses is satisfactory.14 Difficulty Level: Hard 157) How might the following synthesis be carried out: CH2CH3 Benzene C 6 H6 a) C 6 H6 b) several ? steps CH3CH2Cl Cl Cl2 FeCl3 CH3CH2Cl AlCl3 Cl2 FeCl3 AlCl3 product product O C6H6 c) CH3CCl Cl2 H2NNH2 AlCl3 FeCl3 KOH product O C6H6 CH3CCl Zn(Hg) Cl2 AlCl3 HCl FeCl3 d) e) None of these syntheses is satisfactory. Answer: C Topic: Synthesis Section: 15.14 Difficulty Level: Hard 158) How might the following synthesis be carried out: several steps Cl 85 product . Answer: C Topic: Synthesis Section: 15. product Answer: D Topic: Synthesis Section: 15.C 6 H6 a) C 6 H6 b) CH3CH2Cl Cl2 AlCl3 Cl2 FeCl3 CH3CH2Cl FeCl3 AlCl3 product product O C6H6 c) CH3CCl Cl2 Zn(Hg) AlCl3 FeCl3 HCl CH3CCl Zn(Hg) Cl2 AlCl3 HCl FeCl3 product O C6H6 d) e) None of these syntheses is satisfactory.14 Difficulty Level: Hard 159) How might the following synthesis be carried out: several steps Cl C 6 H6 a) C 6 H6 b) CH3CH2Cl AlCl3 Cl2 FeCl3 Cl2 FeCl3 CH3CH2Cl AlCl3 product product O C6H6 c) CH3CCl Cl2 Zn(Hg) AlCl3 FeCl3 HCl product O C6H6 CH3CCl H2NNH2 Cl2 KOH FeCl3 product AlCl3 d) e) None of these syntheses is satisfactory. 86 . 14 Difficulty Level: Hard 160) How might the following synthesis be carried out: several steps Cl C 6 H6 a) C 6 H6 b) CH3CH2Cl Cl2 AlCl3 Cl2 FeCl3 CH3CH2Cl FeCl3 AlCl3 product product O C6H6 c) CH3CCl Cl2 H2NNH2 AlCl3 FeCl3 KOH product O C6H6 H2NNH2 CH3CCl Cl2 product KOH FeCl3 AlCl3 d) e) None of these syntheses is satisfactory. Answer: D Topic: Synthesis Section: 15. hν Br2 KOH CCl4 Fe CH3CH2OH 87 product .14 Difficulty Level: Hard 161) Which is the best sequence of reactions for the preparation of p-bromostyrene from ethylbenzene? ethylbenzene a) NBS.Answer: D Topic: Synthesis Section: 15. 14 Difficulty Level: Hard 162) Which is the best sequence of reactions for the following transformation? O NO2 a) i) HNO3. ii) CH3MgBr. H2SO4.14 Difficulty Level: Hard 163) Which is the best sequence of reactions for the following transformation? O OH NO2 a) i) HNO3. H2O. Answer: A Topic: Synthesis Section: 15. iii) H3O+. heat d) i) HNO3. H2SO4. H2O. ii) LiAlH4. heat e) None of these syntheses is satisfactory. iii) H2O. heat. H2SO4. NH4Cl 88 . ii) H3O+. iii) H3O+. heat b) i) CH3MgBr. hν KOH Fe CCl4 CH3CH2OH b) ethylbenzene NBS. Et2O.ethylbenzene Br2 NBS. hν KOH Br2 CCl4 ZnO CH3CH2OH c) Br2 product ethylbenzene Fe 630 oC d) e) None of these syntheses is satisfactory. H2SO4 c) i) HNO3. product product Fe Answer: B Topic: Synthesis Section: 15. H2SO4. iii) H3O+. iii) HNO3. Et2O. ii) CH3MgBr. ii) NaBH4. Et2O. iii) H3O+. Et2O. H2O. ii) LiAlH4. Et2O. ii) LiAlH4. H2SO4. iii) HNO3. H2O. H2SO4. heat d) i)HNO3. iii) HNO3. Answer: A Topic: Synthesis Section: 15. H2SO4. heat. ii) H3O+. H2O. H2O. heat.14 Difficulty Level: Hard 164) Which is the best sequence of reactions for the following transformation? O OH H NO2 a) i) HNO3. Answer: A Topic: Synthesis Section: 15. H2O.b) i) CH3MgBr. H2SO4. ii) H3O+. heat d) i) HNO3. ii) CH3MgBr. iii) H3O+. iii) H3O+. Et2O. H2SO4. ii) LiAlH4. H2SO4. heat e) None of these syntheses is satisfactory. heat d) i) HNO3. iii) H3O+. NH4Cl b) i) CH3MgBr. ii) NaBH4. heat b) i) CH3MgBr. iii) H3O+.14 Difficulty Level: Hard 165) Which is the best sequence of reactions for the following transformation? O H NO2 a) i) HNO3. H2SO4 c) i) HNO3. ii) NaBH4. heat. ii) H3O+. ii) CH3MgBr. H2SO4. iii) H3O+. heat 89 . ii) NaBH4. H2O. heat e) None of these syntheses is satisfactory. Et2O. H2SO4. iii) H2O. iii) H3O+. iii) HNO3. H2SO4 c) i) HNO3. Et2O. H2SO4 c) i) HNO3. Answer: A Topic: Synthesis Section: 15. H2SO4 c) i) HNO3. H2SO4. Et2O. ii) NaBH4. Et2O. Et2O. H2O. iii) HNO3. iii) 2EtMgBr. ii) H3O+. heat e) None of these syntheses is satisfactory. iii) HNO3. Answer: A Topic: Synthesis Section: 15. H2SO4. H2O.e) None of these syntheses is satisfactory. H2SO4. H2SO4 c) i) HNO3. iii) HNO3. H2SO4. iii) NH4Cl b) i) 2EtMgBr. iii) 2EtMgBr. heat e) None of these syntheses is satisfactory. Et2O d) i) LAH. Et2O d) i) LAH. H2SO4.14 Difficulty Level: Hard 166) Which is the best sequence of reactions for the following transformation? OH O OCH3 NO2 a) i) HNO3. ii) H3O+. Answer: A Topic: Synthesis 90 . iii) HNO3. iii) NH4Cl b) i) 2EtMgBr. H2SO4.14 Difficulty Level: Hard 167) Which is the best sequence of reactions for the following transformation? O OCH3 + NO2 NO2 a) i) HNO3. ii) 2EtLi. ii) 2EtMgBr. ii) 2EtMgBr. ii) 2EtLi. ii) NaBH4. Et2O. Et2O. Et2O. ii) SOCl2.16 Difficulty Level: Medium 91 . H2O e) Two of these syntheses are satisfactory. AlCl3. ii) C6H6. ii) HNO3. iii) Zn(Hg). iv) HNO3. ii) HNO3. H2SO4.Section: 15.HCl d) i) PBr3. NH3(l) EtOH I II III ? V IV a) I b) II c) III d) IV e) V Answer: D Topic: Non-EAS Reactions Section: 15. AlCl3. H2SO4. iv) NaBH4. AlCl3.14 Difficulty Level: Hard 169) What is the Birch reduction product of the following reaction? Na. iv) Zn(Hg). H2SO4. H2SO4 b) i) SOCl2. iii) C6H6.14 Difficulty Level: Hard 168) Which is the best sequence of reactions for the following transformation? O OH NO2 a) i) SOCl2.HCl. iv) H2. AlCl3. Answer: C Topic: Synthesis Section: 15. iii) C6H6. iii) C6H6. Ni c) i) HNO3. A. 92 . A.16 Difficulty Level: Medium 171) The major product(s). of the following reaction. of the following reaction. would be: a) I b) II c) III d) IV e) V Answer: C Topic: Non-EAS Reactions Section: 15.170) The major product(s). 16 Difficulty Level: Medium 172) The major product(s) of the following reaction.would be: a) I b) II c) III d) IV e) V Answer: D Topic: Non-EAS Reactions Section: 15. 93 . 16 Difficulty Level: Medium 173) The major product(s) of the following reaction.would be: a) I b) II c) III d) IV e) V Answer: D Topic: Non-EAS Reactions Section: 15. 94 . e) A mixture of all of these choices.15 Difficulty Level: Medium 174) SN1 solvolysis of C6H5CH=CHCH2Cl in water produces: a) C6H5CH2C(OH)=CH2 b) C6H5CH=CHCH2OH c) C6H5CHOHCH=CH2 d) A mixture of two of these choices.would be: a) I b) II c) III d) IV e) V Answer: E Topic: Non-EAS Reactions Section: 15. Answer: D 95 . 15 Difficulty Level: Medium 176) Which alkyl halide can undergo both SN1 and SN2 reactions in nonacidic solvents? a) CH3Br b) CH3CH2CH2Br CH2 CHCHCH3 Br c) d) C6H5CH2CH2CH2Br CH3 C6H5CCH2Br e) CH3 Answer: C Topic: Non-EAS Reactions Section: 15.15 Difficulty Level: Medium 96 .Topic: Non-EAS Reactions Section: 15.15 Difficulty Level: Medium 175) Which compound is capable of undergoing both SN1 and SN2 reactions in ordinary nonacidic solvents? Br Br Br Br Br I II III IV V a) I b) II c) III d) IV e) V Answer: D Topic: Non-EAS Reactions Section: 15. arenium ion. and c) loss of a ___ to reform the aromatic system. Carbocation Stability Section: 15. proton Topic: EAS Mechanism Section: 15. Answer: electrophile. b) reaction with an aromatic ring to form an ___.8 Difficulty Level: Hard Question type: fill-in-the-blank 97 AlCl4- . These are: a) formation of an ___. there are three steps to an electrophilic aromatic substitution reaction.6 and 15.2 Difficulty Level: Easy Question type: Molecular Drawing 178) Draw a mechanism that explains the formation of the following product in this FriedelCrafts alkylation: AlCl3 + Cl Answer: + AlCl3 C H2 Cl Cl AlCl3 H -H+ Topic: Mechanism.Question type: fill-in-the-blank 177) In general. 10 Difficulty Level: Easy 183) With the exception of halogens.10 Difficulty Level: Easy 181) Electron-donating groups increase the electron density on the aromatic ring. Answer: reactivity. Answer: deactivating Topic: General EAS Reactivity Section: 15.179) When two different groups are present on a benzene ring. meta 98 . the ___ generally determines the outcome of an EAS reaction. causing it to be more reactive than benzene itself towards EAS. These types of groups are called ___ groups.10 Difficulty Level: Easy 182) Electron-withdrawing groups decrease the electron density on the aromatic ring. Answer: activating Topic: General EAS Reactivity Section: 15. causing it to be less reactive than benzene itself towards EAS.14 Difficulty Level: Easy 180) Substituent groups affect both ___ and ___ in electrophilic aromatic substitution reactions. activating groups are ___ directors and deactivating groups are ___ directors. orientation Topic: General EAS Reactivity Section: 15. Answer: more powerful activating group Topic: General EAS Reactivity Section: 15. These types of groups are called ___ groups. Answer: ortho/para. 15. the major product is obtained in good yield. Ring B is more electron-rich due to the electron-donation of both the nitrogen and methyl groups attached versus the two electron-withdrawing carbonyl groups attached to Ring A. What is this major product and why are the minor products not formed to any significant degree? Explain clearly..3. Also.Topic: General EAS Reactivity Section: 15. Due to steric effects. Ring Ring A A O O HN O + Br major products HN O Ring B Br Ring B Topic: General EAS Reactivity Section: 15. bromination mainly occurs on the more electron-rich benzene ring affording a mixture of the following two compounds. does the electrophile E+ attack carbon 2. Therefore. O Br2 FeBr3 HN O ? Answer: The major products are produced by brominating Ring B. bromination ortho to both the nitrogen and methyl group would lead to a minor product. predict the preferential position of attack of an electrophile on furan. i.10 and 15. because Ring A is electron-poor. E 3 E+ 2 or (-H+) E O O 1 Which substitution product forms preferentially and why? 99 O . bromination of this ring would also lead to minor products.10 Difficulty Level: Easy Question type: Essay 184) When the following substance is treated with Br2/FeBr3. which make it inherently electronpoor. and only very small amounts of minor products are found.e.11 Difficulty Level: Medium 185) Based on your knowledge of electrophilic aromatic substitution. or 3? Explain your answer. predict the preferential position of attack of an electrophile on pyrrole.11 Difficulty Level: Hard 186) Based on your knowledge of electrophilic aromatic substitution. only two for the 3 substituted product).. E+ E O E O E O H O H H -H+ E O H H E E+ O O E E -H+ O O Topic: General EAS Reactivity Section: 15. E 3 E+ 2 N H or (-H+) E N H N H 1 Which substitution product forms preferentially and why? Answer: The 2 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses three resonance forms vs.2 and 15. 100 .Answer: The 2 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses three resonance forms vs.e. and hence will form faster. does the electrophile E+ attack carbon 2. or 3? Explain your answer. i. only two for the 3 substituted product). and hence will form faster. i. only two for the 3 substituted product). 101 . does the electrophile E+ attack carbon 2.. E 3 E+ 2 S or + (-H ) E S S 1 Which substitution product forms preferentially and why? Answer: The 2 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses three resonance forms vs.e.E+ E N H N H E N H H E N H H H -H+ E N H H H E E+ N H E E N H -H+ N H N H Topic: General EAS Reactivity Section: 15.11 Difficulty Level: Hard 187) Based on your knowledge of electrophilic aromatic substitution. predict the preferential position of attack of an electrophile on thiophene.2 and 15. and hence will form faster. or 3? Explain your answer. i. 3. predict the position of attack of an electrophile on pyridine. and hence will form faster.E+ E S E S E S H S H H -H+ E S H H E E+ S S E E -H+ S S Topic: General EAS Reactivity Section: 15.. 102 .e.2 and 15. E 4 3 E E+ or 2 N 1 or + (-H ) E N N N Which substitution product(s) forms and why? Answer: The 3 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses three good resonance forms). does the electrophile E+ attack carbon 2.11 Difficulty Level: Hard 188) Based on your knowledge of electrophilic aromatic substitution. or 4? Explain your answer. only one for the 2 substituted product). positively charged nitrogen poor resonance structure Topic: General EAS Reactivity Section: 15.. or 2? Explain your answer. positively charged nitrogen poor resonance structure H H E+ E E N E H E+ H E N N N H H E E N N N N divalent.11 Difficulty Level: Hard 189) Based on your knowledge of electrophilic aromatic substitution. i.H H N N N E+ H N E E E divalent.e.2 and 15. does the NO2+ attack carbon 1. and hence will form faster. NO2 1 2 NO2 NO2+ or (-H+) Which substitution product forms preferentially and why? Answer: The 1 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses two benzylic type resonance forms vs. 103 . predict the preferential position of nitration of naphthalene. explain/illustrate the preferential formation of the 3 substituted product instead of the 2 or 4 product in the electrophilic aromatic substitution of pyridine. and hence will form faster.11 Difficulty Level: Hard 190) Using a potential energy diagram. 104 .H H NO2 NO2 NO2+ the existance of this "homobenzylic"resonance form contributes to the stability of this intermediate NO2 (-H+) H NO2 NO2+ NO2 (-H+) only one benzylic resonance form can be drawn Topic: General EAS Reactivity Section: 15. E 4 N 1 E 3 E+ 2 (-H+) instead of N or N E N Answer: The 3 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses three good resonance forms).2 and 15. 11 Difficulty Level: Hard 191) Using a potential energy diagram. Mechanisms. E + N Reaction Progress Topic: General EAS Reactivity.E.H E ‡ + ‡ + H N N E Ea H Ea P. 105 .2 and 15. only one for the 2 substituted product). NO2 1 2 NO2 NO2+ instead of (-H+) Answer: The 1 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses two benzylic type resonance forms vs. explain/illustrate the preferential formation of the 1 nitrated product instead of the 2 nitrated product in the electrophilic aromatic nitration of naphthalene. Energy Diagrams Section: 15. and hence will form faster. only two for the 3 substituted product).2 and 15.11 Difficulty Level: Hard 192) Using a potential energy diagram. Mechanisms. Energy Diagrams Section: 15. E 3 E+ 2 O instead of (-H+) E O O 1 Answer: The 2 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses three resonance forms vs.Topic: General EAS Reactivity. and hence will form faster 106 . explain/illustrate the preferential formation of the 2 substituted product instead of the 3 product in the electrophilic aromatic substitution of furan. explain/illustrate the preferential formation of the 2 substituted product instead of the 3 product in the electrophilic aromatic substitution of pyrrole. and hence will form faster.Topic: General EAS Reactivity. only two for the 3 substituted product).11 Difficulty Level: Hard 193) Using a potential energy diagram. E 3 E+ 2 N H (-H+) instead of E N H N H 1 Answer: The 2 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses three resonance forms vs. Mechanisms.2 and 15. 107 . Energy Diagrams Section: 15. 2 and 15. explain/illustrate the preferential formation of the 2 substituted product instead of the 3 product in the electrophilic aromatic substitution of thiophene. and hence will form faster. Mechanisms. 108 .Topic: General EAS Reactivity. only two for the 3 substituted product). E 3 E+ instead of 2 S (-H+) E S S Answer: The 2 substitution product is favored since it comes from the arenium ion intermediate that is lower in energy/more stable (possesses three resonance forms vs.11 Difficulty Level: Hard 194) Using a potential energy diagram. Energy Diagrams Section: 15. Mechanisms. H H E E N H E E + N H N H 109 -H+ N H .e. i. since this leads to a carbocation intermediate that can be resonance stabilized through the nitrogen. predict the preferential position of attack of an electrophile.. does the electrophile E+ attack carbon 2. or 3? Explain your answer.2 and 15. E 3 2 E+ (-H+) N H or E N H N H 1 indole Which substitution product forms preferentially and why? Answer: 3-substitution is preferred.Topic: General EAS Reactivity. produces resonance forms without aromaticity. This resonance form is lower in energy than those forming from the 2-substituted product.11 Difficulty Level: Hard 195) Based on your knowledge of electrophilic aromatic substitution. without loss of the benzenoid ring aromaticity. which although can be resonance stabilized through the benzenoid aromatic ring. Energy Diagrams Section: 15. and assuming the pyrrole ring of indole (shown) is activated toward electrophilic aromatic substituted more so than the benzenoid ring. E 3 E+ 2 E + (-H ) O or O O 1 benzo[b]furan Which substitution product forms preferentially and why? Answer: 3-substitution is preferred.. does the electrophile E+ attack carbon 2. produces resonance forms without aromaticity.2 and 15. and assuming the furan ring of benzo[b]furan (shown) is activated toward electrophilic aromatic substituted more so than the benzenoid ring.11 Difficulty Level: Hard 196) Based on your knowledge of electrophilic aromatic substitution. H H E E+ O E E O O 110 + -H O . This resonance form is lower in energy than those forming from the 2-substituted product. or 3? Explain your answer. i.e. since this leads to a carbocation intermediate that can be resonance stabilized through the oxygen. which although can be resonance stabilized through the benzenoid aromatic ring.E+ E E N H N H E N H N H H H E E N H H N H H H -H+ E N H Topic: General EAS Reactivity. Energy Diagrams Section: 15. without loss of the benzenoid ring aromaticity. Mechanisms. predict the preferential position of attack of an electrophile. and assuming the thiophene ring of benzo[b]thiophene (shown) is activated toward electrophilic aromatic substituted more so than the benzenoid ring.e. This resonance form is lower in energy than those forming from the 2-substituted product. which although can be resonance stabilized through the benzenoid aromatic ring. i. produces resonance forms without aromaticity H H E E S E E + S S 111 -H+ S .11 Difficulty Level: Hard 197) Based on your knowledge of electrophilic aromatic substitution.. does the electrophile E+ attack carbon 2. since this leads to a carbocation intermediate that can be resonance stabilized through the oxygen. Mechanisms. or 3? Explain your answer. Energy Diagrams Section: 15. predict the preferential position of attack of an electrophile. E 3 E+ 2 E + (-H ) S or S S 1 benzo[b]thiophene Which substitution product forms preferentially and why? Answer: 3-substitution is preferred.E+ E E O O O H H E E E O O O H H H -H+ O E Topic: General EAS Reactivity.2 and 15. without loss of the benzenoid ring aromaticity. Energy Diagrams Section: 15.2 and 15. E 3 2 S E+ E instead of (-H+) S S 1 benzo[b]thiophene Answer: 3-substitution is preferred. without loss of the benzenoid ring aromaticity. 112 .E+ E E S S S H H E E E S S S H H H -H+ S E Topic: General EAS Reactivity. which although can be resonance stabilized through the benzenoid aromatic ring. explain/illustrate the preferential formation of the 3 substituted product instead of the 2 product in the electrophilic aromatic substitution of benzo[b] thiophene (shown). This resonance form is lower in energy than those forming from the 2-substituted product.11 Difficulty Level: Hard 198) Using a potential energy diagram. Mechanisms. produces resonance forms without aromaticity. since this leads to a carbocation intermediate that can be resonance stabilized through the oxygen. since this leads to a carbocation intermediate that can be resonance stabilized through the oxygen. without loss of the benzenoid ring aromaticity. This resonance form is lower in energy than those forming from the 2-substituted product. E 3 2 O E+ E instead of + (-H ) O O 1 benzo[b]furan Answer: 3-substitution is preferred.E. E S Reaction Progress Topic: General EAS Reactivity. Energy Diagrams Section: 15. explain/illustrate the preferential formation of the 3 substituted product instead of the 2 product in the electrophilic aromatic substitution of benzo[b] furane (shown). Mechanisms. produces resonance forms without aromaticity. which although can be resonance stabilized through the benzenoid aromatic ring.11 Difficulty Level: Hard 199) Using a potential energy diagram. 113 .‡ ‡ E S H Ea H Ea P.2 and 15. which although can be resonance stabilized through the benzenoid aromatic ring. without loss of the benzenoid ring aromaticity. E O Reaction Progress Topic: General EAS Reactivity.2 and 15. produces resonance forms without aromaticity. 114 .E. E 3 2 N H E+ E instead of + (-H ) N H 1 N H indole Answer: 3-substitution is preferred. Mechanisms.11 Difficulty Level: Hard 200) Using a potential energy diagram.‡ ‡ E O H Ea H Ea P. Energy Diagrams Section: 15. since this leads to a carbocation intermediate that can be resonance stabilized through the nitrogen. This resonance form is lower in energy than those forming from the 2-substituted product. explain/illustrate the preferential formation of the 3 substituted product instead of the 2 product in the electrophilic aromatic substitution of indole (shown). Explain clearly. is in accordance with the general trend that acid catalyzed hydration chiefly tends to afford products formed via the most stable intermediate carbocation. is not detected at all. one is also benzylic and thus stabilized by resonance.2 and 15.‡ ‡ E N H Ea H H P. 115 . the relative stabilities of the two possible carbocation intermediates is significantly different: although both are secondary carbocations.11 Difficulty Level: Hard 201) Acid-catalyzed hydration of 1-phenyl-1-pentene gives 1-phenyl-1-pentanol almost exclusively. almost exclusively. 1-phenyl-2-pentanol. Ea E N H Reaction Progress Topic: General EAS Reactivity. The observation that 1phenyl-1-pentene gives 1-phenyl-1-pentanol. Answer: Acid catalyzed hydration of an alkene occurs through a carbocation intermediate. Energy Diagrams Section: 15. Although 1-phenyl-1-pentene is symmetrically substituted at the C=C. the other possible hydration product. Mechanisms.E. when the reaction is carried out without catalyst. not formed to any almost exclusively appreciable degree OH H + H chief product OH not detected Topic: Mechanism.H 2O H + H 3 O+ + H + 2o.director.p. Explain clearly. the methyl group undergoes freeradical halogenation via the benzyl radical intermediate. Carbocation Stability Section: 15.and ppositions.12 Difficulty Level: Medium 203) Suggest a reasonable synthetic strategy for the synthesis of 3. 116 .3 and 15. or without catalyst.5-dinitrobenzyl alcohol from benzaldehyde.formed 2o. the identity of the major product(s) obtained depends on whether the reaction is carried out in the presence of catalytic amounts of FeCl3. at high temp. In contrast. at high temperature. o-. Cl2 FeCl3 Cl Cl + Cl Cl2 heat Topic: EAS/non-EAS Reactivity Section: 15.12 Difficulty Level: Hard 202) When toluene reacts with Cl2. since the methyl group in toluene is an activating. Answer: Reaction with Cl2/FeCl3 results in electrophilic aromatic substitution at the o. benzylic: stabilized by resonance. but not benzylic: less stable. 7 Difficulty Level: Medium 205) Suggest a reasonable synthetic strategy for the synthesis of 6-methyl-3-phenyl-3-heptanol from 4-methylpentanoyl chloride. (CH3)2CHCH2CH2COCl O OH NaBH4 H 2O Cl O AlCl3 Answer: 4-methylpentanoyl chloride 4-methyl-1-phenyl-1-pentanol Topic: Synthetic Strategy Section: 15. 117 .14 Difficulty Level: Medium 204) Suggest a reasonable synthetic strategy for the synthesis of 4-methyl-1-phenyl-1-pentanol from 4-methylpentanoyl chloride.5-dinitrobenzyl alcohol Topic: Synthetic Strategy Section: 15. (CH3)2CHCH2CH2COCl O O OH i) C2H 5MgBr ii) NH 4Cl Cl AlCl3 Answer: 4-methylpentanoyl chloride 6-methyl-3-phenyl-3-heptanol Topic: Synthetic Strategy Section: 15.14 Difficulty Level: Hard 206) What product would result from the following series of reactions.O NO2 HNO3 (excess) H2SO4 O2N heat O Answer: benzaldehyde NaBH4 H 2O NO2 OH O2N 3. HF Answer: O Br2. ether H 3O + (-H2O) Topic: Synthetic Strategy Section: 15. heat (-H2O 9. Br2. Mg. FeBr3 OH MgBr Br Mg. ether H3O+ PBr3 O Br MgBr HF Mg. ethylene oxide 4.14 Difficulty Level: Hard 207) Propose a reasonable synthesis of the following compound from benzene. PBr3 6. Mg. ether 3. FeBr3 2. multi-step process Answer: 118 . ether 7.1. H3O+ 5. H3O+. O ? 8. O Br2. ether H 3O + (-H2O) Topic: Synthetic Strategy Section: 15. SOCl2 O ? + 3. ether H3O+ PBr3 O Br MgBr HF Mg. AlCl3 O Answer: O O SOCl2 AlCl3 O + COOH O O O AlCl3 COCl O Topic: Synthetic Strategy Section: 15.14 Difficulty Level: Hard 208) What product would result from the following series of reactions: O 1.14 Difficulty Level: Hard 119 . FeBr3 OH MgBr Br Mg. AlCl3 2.