Structure and Nomenclature. Chemistry TEST BANK. Chapter Eleven. All Answers highlighted.

Chemistry: Structure and Nomenclature Chapter Eleven MULTIPLE CHOICE QUESTIONS Topic: Structure and Nomenclature Section: 5.3 and 11.1 Difficulty Level: Hard 1. What is the relationship between alcohols I and II? CH3 OH CH3 HO

I

II

They are: A) different conformations of the same compound.

B) constitutional isomers.

C) enantiomers.

D) diastereomers.

E) identical.

Ans: C

191

Topic: Structure and Nomenclature Section: 5.3 and 11.1 Difficulty Level: Hard 2. What is the relationship between alcohols I and II? CH3

CH3

OH

OH

I II They are: A) different conformations of the same compound.

B) constitutional isomers.

C) enantiomers.

D) diastereomers.

E) identical.

Ans: C Topic: Structure and Nomenclature Section: 5.3 and 11.1 Difficulty Level: Hard 3. What is the relationship between alcohols I and II? OH

CH3

OH

CH3

I II They are: A) different conformations of the same compound.

B) constitutional isomers.

C) enantiomers.

D) diastereomers.

E) identical.

Ans: C

192

Topic: Structure and Nomenclature Section: 5.3 and 11.1 Difficulty Level: Hard 4. What is the relationship between alcohols I and II? H

CH3 CH3 OH

H

H

H

OH

I II They are: A) different conformations of the same compound.

B) constitutional isomers.

C) enantiomers.

D) diastereomers.

E) identical.

Ans: C

Topic: Structure and Nomenclature Section: 5.12 and 11.1 Difficulty Level: Hard 5. What is the relationship between alcohols I and II? H

H CH3 OH

H

H

CH3

OH

I II They are: A) different conformations of the same compound.

B) constitutional isomers.

C) enantiomers.

D) diastereomers.

E) identical.

Ans: D

193

Topic: Structure and Nomenclature Section: 5.12 and 11.1 Difficulty Level: Hard 6. What is the relationship between alcohols I and II? CH3

CH3 HO

HO

I

II

They are: A) different conformations of the same compound.

B) constitutional isomers.

C) enantiomers.

D) diastereomers.

E) identical.

Ans: D Topic: Structure and Nomenclature Section: 5.12 and 11.1 Difficulty Level: Hard 7. What is the relationship between alcohols I and II? CH3

CH3

OH

I

OH

II

They are: A) different conformations of the same compound.

B) constitutional isomers.

C) enantiomers.

D) diastereomers.

E) identical.

Ans: D

194

Topic: Nomenclature Section: 11.1A Difficulty Level: Easy 8. What is the correct IUPAC name for the following compound?

CH3 CH3CHOHCHCHCH(CH3)2 CH3 A) 4-isopropyl-3,4-dimethyl-2-butanol B) 2,3,4-trimethyl-4-pentanol C) 1,1,2,3-tetramethyl-4-pentanol D) 3,4,5-trimethyl-2-hexanol E) 3,4,5,5-tetramethyl-2-pentanol Ans: D Topic: Nomenclature Section: 11.1A Difficulty Level: Easy 9. A correct IUPAC name for isobutyl alcohol is: A) 2-Methyl-1-propanol B) 2-Methyl-1-butanol C) 1-Methyl-1-propanol D) 1,1-Dimethyl-1-ethanol E) 3-Methyl-1-propanol Ans: A Topic: Nomenclature Section: 11.1A Difficulty Level: Easy 10.

CH2CH3 CH3CH2COH

The IUPAC name of compound A) 1,1,1-Triethylmethanol B) 1,1-Diethyl-1-propanol C) 2-Ethyl-3-pentanol D) 3-Ethyl-3-pentanol E) tert-Heptanol Ans: D

CH2CH3

195

is:

Topic: Nomenclature Section: 11.1A Difficulty Level: Medium 11. What is the correct IUPAC name for the following compound?

CH3 CH3CH2C=CCH2CH3 CH2CH2OH A) 3-methyl-4-ethyl-3-hexen-6-ol B) 4-ethyl-3-methyl-3,6-hexenol C) 3-ethyl-4-methyl-3-hexen-1-ol D) 3-methyl-4-(2-hydroxyethyl)-3-hexene E) 3-(2-hydroxyethyl)- 3-methyl-3-hexene Ans: C Topic: Nomenclature Section: 11.1A Difficulty Level: Medium 12. What is a correct IUPAC name for the following compound?

HO

OH

A) 1,2-butanediol B) isopropanol C) 1-propanol D) 1,2-propanediol E) Ethylene glycol Ans: D

196

Topic: Nomenclature Section: 11.1A Difficulty Level: Medium 13. What is a correct IUPAC name for the following compound?

HO

OH

A) 1,2-butanediol B) isopropanol C) 1-proanol D) Propylene glycol E) 1,2-ethanediol Ans: E Topic: Nomenclature Section: 11.1A Difficulty Level: Medium 14. The correct IUPAC name for tert-butyl alcohol is: A) 1-Butanol B) 2-Methyl-1-propanol C) 2-Methyl-2-propanol D) 2-Butanol E) 1,1-Dimethyl-1-ethanol Ans: C Topic: Nomenclature Section: 11.1A Difficulty Level: Medium 15. 2,2-Dimethyl-1-propanol has the common name: A) Isoamyl alcohol B) Isopentyl alcohol C) tert-Pentyl alcohol D) Neopentyl alcohol E) 2-Methylisobutyl alcohol Ans: D

197

Topic: Nomenclature Section: 11.1A Difficulty Level: Medium 16. Which of these, though often used, is an incorrect common name for CH3CHOHCH3?

A) Isopropyl alcohol B) sec-Propyl alcohol C) 2-Propanol D) Isopropanol E) More than one of these.

Ans: D Topic: Nomenclature Section: 11.1A Difficulty Level: Medium 17. Which of these, though often used, is an incorrect common name for (CH3)3COH? A) tert-Butyl alcohol B) tert-Butanol C) 2-Methyl-2-propanol D) More than one is incorrect.

E) Each is a correct name.

Ans: B Topic: Isomerism, Stereoisomers Section: 11.1A Difficulty Level: Medium 18. Which of the following can be described as “optically active, primary alcohol”?

A) CH3CH2CH2CH2CH2OH B) (CH3)2CHCH2CH2OH C) CH3CH2CH(CH3)CH2OH D) (CH3)2CHCHOHCH3 E) Two of the above Ans: C

198

Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 19.

OH

The correct IUPAC substitutive name for A) 4-Penten-2-methyl-2-ol B) 4-Methyl-1-penten-2-ol C) 2-Methyl-4-penten-2-ol D) 4-Methyl-1-penten-4-ol E) 4-Hydroxy-4-methyl-1-pentene Ans: C Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 20.

OH OH

is properly named: A) cis-1,2-Cyclopentanediol B) meso-1,2-Cyclopentanediol C) (1R,2R)-1,2-Cyclopentanediol D) (1R,2S)-1,2-Cyclopentanediol E) (1S,2S)-1,2-Cyclopentanediol Ans: C

199

is:

Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 21.

OH

OH

is properly named: A) 1,2-Cyclopentanediol B) 1,5-Cyclopentanediol C) (1R,2R)-1,2-Cyclopentanediol D) (1R,2S)-1,2-Cyclopentanediol E) (1S,2S)-1,2-Cyclopentanediol Ans: D Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 22.

OH OH

is properly named: A) cis-1,2-Cyclohexanediol B) meso-1,2-Cyclohexanediol C) (1R,2R)-1,2-Cyclohexanediol D) (1R,2S)-1,2-Cyclohexanediol E) (1S,2S)-1,2-Cyclohexanediol Ans: C

200

Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 23.

OH OH

is properly named: A) 1,2-Cyclohexanediol B) 1,6-Cyclohexanediol C) (1R,2R)-1,2-Cyclohexanediol D) (1R,2S)-1,2-Cyclohexanediol E) (1S,2S)-1,2-Cyclohexanediol Ans: D Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 24.

OH

OH

is properly named: A) 1,3-Cyclopentanediol B) 1,4-Cyclopentanediol C) (1R,3R)-1,3-Cyclopentanediol D) (1R,3S)-1,3-Cyclopentanediol E) (1S,3S)-1,3-Cyclopentanediol Ans: C

201

Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 25.

HO

OH

is properly named: A) 1,4-Cycloheptanediol B) 1,5-Cycloheptanediol C) (1R,4R)-1,4-Cycloheptanediol D) (1R,4S)-1,4-Cycloheptanediol E) (1S,4S)-1,4-Cycloheptanediol Ans: D Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 26. A correct name for the following Fischer projection formula is: OH H3C

C

C

CH3 H

A) (R)-3-Pentyn-2-ol B) (S)-3-Pentyn-2-ol C) (R)-2-Pentyn-4-ol D) (S)-2-Pentyn-4-ol E) (S)-2-Hydroxy-3-pentyne Ans: B

202

Topic: Stereoisomerism Section: 11.1B Difficulty Level: Easy 27. What is the relationship between alcohols I and II? CH3

CH3 HO OH

I

II

They are: A) different conformations of the same compound.

B) constitutional isomers.

C) enantiomers.

D) diastereomers.

E) identical.

Ans: B

203

Topic: Nomenclature Section: 11.1B Difficulty Level: Medium 28. Select the structure of benzyl methyl ether.

I

CH3

II

CH3O

III

CH3 O CH2

IV

O

CH O CH CH3

V

CH3

CH3

CH3 CH2

O

CH2

CH3

A) I B) II C) III D) IV E) V Ans: C Topic: Nomenclature Section: 11.1B Difficulty Level: Medium 29. Which is a correct IUPAC name for CH3CH2OCH2CH2CH2OCH2CH3?

A) 1,4-Dioxane B) Ethylene glycol diethyl ether C) 1,3-Diethoxypropane D) 1,2-Diethoxyethane E) 1,2-Diethoxymethane Ans: C

204

Topic: Isomerism, Stereoisomers Section: 11.1B Difficulty Level: Medium 30. What is the total number of pentyl alcohols, including stereoisomers?

A) 7 B) 8 C) 9 D) 10 E) 11 Ans: E Topic: Isomerism, Stereoisomers Section: 11.1B Difficulty Level: Medium 31. The number of primary alcohols corresponding to the formula C5H12O, counting stereoisomers separately, is: A) 1 B) 2 C) 3 D) 4 E) 5 Ans: E Topic: Isomerism, Stereoisomers Section: 11.1B Difficulty Level: Medium 32. The number of tertiary alcohols corresponding to the formula C5H12O, counting stereoisomers separately, is: A) 1 B) 2 C) 3 D) 4 E) 5 Ans: A

205

Topic: Isomerism, Stereoisomers Section: 11.1B Difficulty Level: Medium 33. The number of secondary alcohols corresponding to the formula C5H12O, counting stereoisomers separately, is: A) 1 B) 2 C) 3 D) 4 E) 5 Ans: E Topic: Isomerism, Stereoisomers Section: 11.1B Difficulty Level: Medium 34. The total number of ethers corresponding to the formula C5H12O, counting stereoisomers separately, is: A) 4 B) 5 C) 6 D) 7 E) 8 Ans: D Topic: Isomerism, Stereoisomers Section: 11.1B Difficulty Level: Medium 35. The number of optically active pentyl alcohols (C5H11OH), i.e., the total number of individual enantiomers, is: A) 0 B) 2 C) 3 D) 4 E) 6 Ans: E

206

Topic: Nomenclature Section: 11.1B Difficulty Level: Hard 36. What is the most accurate name for the molecule represented by the following Fischer projection formula?

H3CH2C

H

OCH3 CH3

A) sec-Butyl methyl ether B) Isobutyl methyl ether C) tert-Butyl methyl ether D) (R)-2-Methoxybutane E) (S)-2-Methoxybutane Ans: E Topic: Physical Properties, Comparison Section: 11.2 Difficulty Level: Easy 37. Which of the compounds listed below would you expect to have the highest boiling point? (They all have approximately the same molecular weight.)

A) CH3CH2CH2CH2CH3 B) CH3CH2CH2CH2OH C) CH3CH2CH2OCH3 D) CH3CH2CH2Cl E) CH3CH2OCH2CH3 Ans: B Topic: Physical Properties, Comparison Section: 11.2 Difficulty Level: Easy 38. Which compound would have the highest boiling point?

A) CH3CH2CH2CH3 B) CH3CH2OCH3 C) CH3CH2CH2OH D) (CH3)2CHOH E) HOCH2CH2OH Ans: E

207

Topic: Physical Properties, Comparison Section: 11.2 Difficulty Level: Easy 39. Which compound would have the lowest boiling point?

A) CH3CH2CH2CH3 B) CH3CH2OCH2CH3 C) CH3CH2CH2OH D) (CH3)2CHOH E) HOCH2CH2OH Ans: A Topic: Physical Properties, Comparison Section: 11.2 Difficulty Level: Easy 40. Which compound would have the highest boiling point?

A) CH3CH2CH2CH3 B) CH2(OH)CH(OH)CH2OH C) CH3CH2CH2OH D) (CH3)2CHOH E) HOCH2CH2OH Ans: B Topic: Physical Properties, Comparison Section: 11.2 Difficulty Level: Easy 41. Which compound would have the lowest solubility in water?

A) Diethyl ether B) Methyl propyl ether C) 1-Butanol D) 2-Butanol E) Pentane Ans: E

208

Topic: Physical Properties, Comparison Section: 11.2 Difficulty Level: Easy 42. Which compound would have the greatest solubility in water?

A) Diethyl ether B) Methyl propyl ether C) 1-Butanol D) 1,2-Butanediol E) Pentane Ans: D Topic: Physical Properties, Comparison Section: 11.2 Difficulty Level: Easy 43. Which compound would have the lowest boiling point?

O

I

OH

OH

II

III

A) I B) II C) III D) IV E) V Ans: A

209

CH2OH

IV

OH

V

Topic: Physical Properties, Comparison Section: 11.2 Difficulty Level: Easy 44. Which compound would have the highest boiling point?

O

O

O

O

O

OH

I

II

III OH

O O

IV

OH

V

A) I B) II C) III D) IV E) V Ans: E Topic: Ether Reactivity Section: 11.2 Difficulty Level: Easy 45. Which of the following statements is NOT true of ethers?

A) Ethers are generally unreactive molecules toward reagents other than strong acids.

B) Ethers generally have lower boiling points than alcohols of a corresponding molecular weight.

C) Ethers generally have much lower water solubilities than alcohols with a corresponding molecular weight.

D) Ethers can generally be cleaved by heating them with strong acids.

E) Ethers form peroxides when allowed to stand in the presence of oxygen.

Ans: C

210

Topic: General Section: 11.3A Difficulty Level: Easy 46. The major industrial process in use today for the production of methanol is the: A) hydration of ethyne.

B) distillation of wood.

C) hydrogenation of carbon dioxide.

D) reduction of methanal.

E) catalytic reduction of carbon monoxide.

Ans: E Topic: General Section: 11.3B Difficulty Level: Easy 47. Today, most industrial ethanol is made in the U.S. by the: A) fermentation of grain.

B) hydrolysis of ethyl bromide.

C) hydration of ethylene.

D) reduction of acetaldehyde.

E) hydration of acetylene.

Ans: C Topic: Ether Reaction Rates Section: 11.3D Difficulty Level: Easy 48. Which of these ethers is most resistant to peroxide formation on exposure to atmospheric oxygen?

A) CH3OCH2CH3 B) CH3CH2OCH2CH3 C) (CH3)2CHOCH(CH3)2 D) (CH3)2CHOCH2CH3 E) CH3OC(CH3)3 Ans: E

211

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Easy 49. Which product(s) would you expect to obtain from the following sequence of reactions?

CH3

1. BH3-THF

?

2. H2O2, NaOH CH3 CH3 OH

I

CH3

H3C O

OH

OH

+ enantiomer

+ enantiomer

+ enantiomer

III

IV

II

A) I B) II C) III D) IV E) V Ans: C

212

CH2OH

V

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Easy 50. Select the structure of the major product formed from the following reaction.

CH3

1. Hg(OOCCH3)2 THF, H2O

?

2. NaBH4, NaOH CH3

OH

CH3

CH2OH

HO CH3

CH3 OH

OH

I

II

III

IV

V

A) I B) II C) III D) IV E) V Ans: D Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Easy 51. Anti-Markovnikov hydration of the carbon-carbon double bond occurs when an alkene reacts with: A) BH3:THF; then H2O2/OHB) BH3:THF; then CH3COOH C) Hg(OAc)2, THF, H2O; then NaBH4, OHD) Hg(OAc)2, THF, CH3OH; then NaBH4, OHE) Hg(OAc)2, THF, H2O; then BH3:THF Ans: A

213

Topic: Reaction Mechanisms Section: 11.4 Difficulty Level: Easy 52. Which statement is true concerning the formation of alcohols by the hydroborationoxidation sequence?

A) Overall, the process results in syn addition and anti-Markovnikov orientation.

B) Overall, the process results in anti addition and anti-Markovnikov orientation.

C) Overall, the process results in syn addition and Markovnikov orientation.

D) Overall, the process results in anti addition and Markovnikov orientation.

E) The stereochemistry and orientation are unpredictable.

Ans: A Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Medium 53. Which would be the best way to carry out the following synthesis? ?

CH3CH2CHCH3

CH3CH2CH2CH2OH

Br

A) (1) HA, heat; (2) H3O+, H2O, heat B) (1) (CH3)3COK / (CH3)3COH; (2) BH3:THF, then H2O2, OHC) (1) (CH3)3COK / (CH3)3COH; (2) H3O+, then H2O, heat D) (1) KOH, C2H5OH; (2) BH3:THF, then H2O2, OHE) (1) KOH, C2H5OH; (2) HA, heat; (3) H3O+, H2O, heat Ans: B

214

Topic: Alcohol Synthesis, Mechanisms Section: 11.4 Difficulty Level: Medium 54. Select the potential energy diagram that best represents the following reaction: H+

OH

H2O

A) I B) II C) III D) IV E) V Ans: D

215

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Medium 55. Which reaction can accomplish the following transformation in good yield: ?

OH

A) H+/H2O B) oxymercuration/demercuation C) hydroboration/oxidation D) Reaction with NaOH E) None of the above Ans: B Topic: Alcohol Synthesis, Isotope Labeling Section: 11.4 Difficulty Level: Medium 56. The hydroboration-oxidation procedure can be successfully employed for synthesis of deuterated derivatives, by using BD3 instead of BH3. What product would you expect from the following reaction?

CH3

1. (BD3)2

?

2. H2O2/NaOH HO H

D

H CH3

+ enantiomer I

H

D

BD2 CH3

+ enantiomer II

D

D CH3

H

+ enantiomer III

A) I B) II C) III D) IV E) V Ans: A

216

H

OH CH3

+ enantiomer IV

H D

BD2 CH3

+ enantiomer V

Topic: Alcohol Synthesis, Isotope Labeling Section: 11.4 Difficulty Level: Medium 57. The oxymercuration-demercuration procedure can be successfully employed for synthesis of deuterated derivatives, by using NaBD4 instead of NaBH4 in the second step. What product would you expect from the following reaction?

1. Hg(OAc)2/H2O

?

2. NaBD4, NaOH

OH OH

I

II

OH

OH

D

III

D

D

OH

IV

V

A) I B) II C) III D) IV E) V Ans: C Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Medium 58. Which of the following would be a reasonable synthesis of 2-butanol?

A) RCOOH 1-Butene 1. BH3-THF B) 1-Butene 2. H2O2, NaOH 1. Hg(OAc)2, THF, H2O C) 1-Butene 2. NaBH4, NaOH D) 1. Ha(OAc)2/CH3OH 1-Butene 2. NaBH4, NaOH E) None of these Ans: C

217

218

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Medium 59. Which of the following would be a reasonable synthesis of CH3CH2CH2CH2OH? A) H3O+, heat 1-Butene 1. BH3-THF B) 1-Butene 2. H2O2, NaOH 1. Hg(OAc)2, THF, H2O C) 1-Butene 2. NaBH4, NaOH D) 1. Ha(OAc)2/CH3OH 1-Butene 2. NaBH4, NaOH E) None of these Ans: B Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Medium 60. Which would be the major product of the reaction shown?

CH2CH3

1. Hg(OAc)2, THF, H2O

?

2. NaBH4, NaOH

H

OH

OHCH2CH3

H

H CH2CH3

H

CH2CH3 H CH2CH3

H CH2CH2OH

O

H

H

H

OH

H

I

II

III

IV

V

A) I B) II C) III D) IV E) V Ans: B

219

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Medium 61. What is the major product of the reaction: i) BH3, THF ii) H2O2,NaOH CH3 CH3

?

CH3

OH

+ enantiomer I

CH3 OH

OH

II

III

+ enantiomer IV

A) I B) II C) III **** D) IV E) Both III and IV Ans: D Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Medium 62. Oxymercuration-demercuration of 3-methylcyclopentene produces this/these product(s): HO CH3

CH2OH

CH3

CH3 OH OH

I

II

III

IV

A) I B) II C) III D) IV E) Both III and IV Ans: E

220

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Hard 63. What is the major product of the reaction when (R)-3-methylcyclohexene is subjected to the hydroboration-oxidation sequence?

A) (1R,2R)-2-methylcyclohexanol + (1S,2R)-2-methylcyclohexanol B) (1S,2R)-2-methylcyclohexanol + (1S,2S)-2-methylcyclohexanol C) (1R,3R)-3-methylcyclohexanol + (1S,3R)-3-methylcyclohexanol D) (1S,3R)-3-methylcyclohexanol (1S,3S)-3-methylcyclohexanol E) Two of the above Ans: E Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Hard 64. Which would be the best method for converting 3,3-dimethyl-1-pentene into 3,3dimethyl-2-pentanol?

A) H3O+, heat B) BH3:THF; then H2O2, OHC) concd. H2SO4; then H2O, heat D) Hg(OAc)2/THF-H2O; then NaBH4,OHE) HBr; then NaOH/H2O Ans: D

221

Topic: Alcohol Synthesis, Mechanisms Section: 11.4 Difficulty Level: Hard 65. Assuming an overall exothermic process, select the potential energy diagram that best represents the following reaction: H+

HO

H2O

A) I B) II C) III D) IV E) V Ans: E

222

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Hard 66. Select the structure of the major product formed from the following reaction.

H3O+

?

OH OH OH

III

II

I

OH OH

IV

V

A) I B) II C) III D) IV E) V Ans: C

223

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Hard 67. Select the structure of the major product formed from the following reaction.

H3O+

?

OH

OH OH

II

I

III

OH

OH

IV

IV

A) I B) II C) III D) IV E) V Ans: C

224

Topic: Reaction Mechanisms Section: 8.6 and 11.4 Difficulty Level: Medium 68. What is the electrophilic species involved in the initial step of the reaction below?

Hg(OAc)2

OH HgOAc

THF, H2O +

A) OH B) +HgOAc C) H3O+ D) THF E) the THF/H2O complex Ans: B Topic: Reaction Mechanisms Section: 8.6 and 11.4 Difficulty Level: Medium 69. What is the nucleophilic species involved in the initial step of the reaction below?

Hg(OAc)2

OH HgOAc

THF, H2O

A) -OH B) Hg(OAc)2 C) H2O D) cyclopentene E) the THF/H2O complex Ans: D Topic: Alcohol Reaction Rates Section: 11.8 Difficulty Level: Easy 70. Which of the alcohols listed below would you expect to react most rapidly with HBr? A) CH3CH2CH2CH2CH2CH2OH B) (CH3CH2)2CH2CH2OH C) (CH3CH2)2CHOHCH3 D) CH3CH2CH2CH2CH2OH E) (CH3CH2)2C(CH3)OH Ans: E

225

Topic: Alcohol Reaction Rates Section: 11.8 Difficulty Level: Medium 71. Which alcohol would undergo acid-catalyzed dehydration most rapidly?

A) 3,3-dimethyl-1-butanol B) 2,2-dimethyl-1-butanol C) 3,3-dimethyl-2-butanol D) 2-methyl-2-butanol E) All would undergo dehydration equally rapidly.

Ans: D Topic: Alcohol Reactions Section: 11.8A Difficulty Level: Easy 72. Which of the following could not be used to synthesize 2-bromopentane efficiently?

A) 1-Pentene + HBr  B) 2-Pentene + HBr  C) 2-Pentanol + HBr  D) 2-Pentanol + PBr3  E) All of the above would afford good yields of 2-bromopentane.

Ans: B Topic: Alcohol Reaction Rates Section: 11.8A Difficulty Level: Easy 73. Which of these alkyl halide syntheses is predicted to occur at the greatest rate?

A) CH3CH2CH2CH2OH + HI → B) (CH3)2CHCH2OH + HBr → C) CH3CHOHCH2CH3 + HCl → D) CH3CHOHCH2CH3 + HBr → E) (CH3)3COH + HI → Ans: E

226

Topic: Reaction Mechanisms Section: 11.8A Difficulty Level: Easy 74. The following reaction, CH3CH2CH2CH2OH

HBr

CH3CH2CH2CH2Br

heat

+

H 2O

is probably: A) an SN1-type reaction involving the protonated alcohol as the substrate.

B) an SN2-type reaction involving the protonated alcohol as the substrate.

C) an E1-type reaction involving the protonated alcohol as the substrate.

D) an E2-type reaction involving the protonated alcohol as the substrate.

E) an epoxidation reaction.

Ans: B Topic: Reaction Mechanisms Section: 11.8A Difficulty Level: Medium 75. The reaction between 1-pentanol and HBr to yield 1-bromopentanol is probably: A) an SN1-type reaction involving the protonated alcohol as the substrate.

B) an SN2-type reaction involving the protonated alcohol as the substrate.

C) an E1-type reaction involving the protonated alcohol as the substrate.

D) an E2-type reaction involving the protonated alcohol as the substrate.

E) an epoxidation reaction.

Ans: B Topic: Reaction Mechanisms Section: 11.8A Difficulty Level: Medium 76. The reaction between 2-methyl-2-pentanol and HBr to yield 2-bromo-2-methylpentane is probably: A) an SN1-type reaction involving the protonated alcohol as the substrate.

B) an SN2-type reaction involving the protonated alcohol as the substrate.

C) an E1-type reaction involving the protonated alcohol as the substrate.

D) an E2-type reaction involving the protonated alcohol as the substrate.

E) an epoxidation reaction.

Ans: A

227

Topic: Reaction Mechanisms Section: 11.8A Difficulty Level: Medium 77. The reaction between 2-methyl-2-pentanol and HBr to yield 2-methyl-2-pentene is probably: A) an SN1-type reaction involving the protonated alcohol as the substrate.

B) an SN2-type reaction involving the protonated alcohol as the substrate.

C) an E1-type reaction involving the protonated alcohol as the substrate.

D) an E2-type reaction involving the protonated alcohol as the substrate.

E) an epoxidation reaction.

Ans: C Topic: Reaction Mechanisms Section: 11.8A Difficulty Level: Medium 78. The reaction between 4-methyl-1-pentanol and HBr to yield 4-methyl-1-pentene is probably: A) an SN1-type reaction involving the protonated alcohol as the substrate.

B) an SN2-type reaction involving the protonated alcohol as the substrate.

C) an E1-type reaction involving the protonated alcohol as the substrate.

D) an E2-type reaction involving the protonated alcohol as the substrate.

E) an epoxidation reaction.

Ans: D

228

Topic: Alcohol Reactions, Mechanisms Section: 11.8A Difficulty Level: Medium 79. Assuming an overall exothermic process, select the potential energy diagram that best represents the following reaction: OH

H+ heat (-H2O)

A) I B) II C) III D) IV E) V Ans: B

229

Topic: Alcohol Reactions Section: 11.8A Difficulty Level: Medium 80. Which of the following could be used to synthesize 2-bromobutane?

A) CH3CH2CH= CH2 + Br2 (aq) → B) CH3CH2CΗΟΗCH3 + HBr → C) CH3CH2C≡ CH + HBr → D) CH3CH2C≡ CH + Br2 → E) More than one of the above Ans: B Topic: Alcohol Reactions Section: 11.8A Difficulty Level: Medium 81. Which of the following could be used to synthesize 2-iodobutane?

A) CH3CH2CH= CH2 + I2 (aq) → B) CH3CH2CΗΟΗCH3 + HI → C) CH3CH2C≡ CH + HI → D) CH3CH2C≡ CH + I2 → E) None of the above Ans: B Topic: Alcohol Reactions Section: 11.8A Difficulty Level: Medium 82. Which of the following could be used to synthesize 2-chlorobutane?

A) CH3CH2CH= CH2 + Cl2 (aq) → B) CH3CH2CΗΟΗCH3 + HCl → C) CH3CH2C≡ CH + HCl → D) CH3CH2C≡ CH + Cl2 → E) None of the above Ans: B

230

Topic: Alcohol Reaction Rates Section: 11.9 Difficulty Level: Easy 83. Which of the alcohols listed below would you expect to react most rapidly with PBr3?

A) CH3CH2CH2CH2CH2CH2OH B) (CH3CH2)2CH(OH)CH2CH3 C) (CH3CH2)2CHOHCH3 D) (CH3CH2)3COH E) (CH3CH2)2C(CH3)OH Ans: A Topic: Alcohol Reactions Section: 11.9 Difficulty Level: Medium 84. Which of the following could be used to synthesize 1-bromobutane efficiently?

A) CH3CH2CH=CH2 + HBr → B) CH3CH2CH2CH2OH + PBr3 → C) CH3CH2CH2(OH)CH3 + HBr → D) CH3CH2CH2CH2OH + Br2 → E) None of these Ans: B Topic: Alcohol Reactions Section: 11.9 Difficulty Level: Medium 85. Which of the following could be used to synthesize 1-bromopentane?

A) CH3CH2CH2CH=CH2 + HBr → B) CH3CH2CH2CH2CH2OH + PBr3 → C) CH3CH2CH2CH2CH2OH + NaBr → D) CH3CH2CH2CH2CH2OH + Br2 → E) CH3CH2CH2CH=CH2 + Br2 → Ans: B

231

Topic: Alcohol Reactions Section: 11.9 Difficulty Level: Medium CH3

86.

H3C

CH

CH3 CH

CH3

to

H3C

CH

CH

CH3

OH Br The conversion of is best achieved through use of which of these reagents in a low temperature reaction?

A) Concd. HBr B) Br2 C) NaBr, H2SO4 D) PBr3 E) HBr, peroxide Ans: D

Topic: Alcohol Reactions Section: 11.9 Difficulty Level: Medium 87. The conversion of 3-methyl-1-octanol to 1-chloro-3-methyloctane is best achieved through use of which of these reagents?

A) Concd. HCl B) SO2Cl2 C) NaCl, H2SO4 D) PCl3 E) POCl3 Ans: D Topic: Reaction Mechanisms Section: 11.9 Difficulty Level: Medium 88. The reaction between 4-methyl-1-pentanol and PBr3 to yield 1-bromo-4-methylpentane is probably: A) an SN1-type reaction involving the protonated alkyl dibomophosphite of the alcohol as the substrate.

B) an SN2-type reaction involving the protonated alkyl dibomophosphite of the alcohol as the substrate.

C) an E1-type reaction involving the protonated alkyl dibomophosphite of the alcohol as the substrate.

D) an E2-type reaction involving the protonated alkyl dibomophosphite of the alcohol as the substrate.

E) an epoxidation reaction.

Ans: B

232

Topic: Alcohol Reactions Section: 11.8 and 11.9 Difficulty Level: Medium 89. Which of the following reactions would serve as a synthesis of butyl bromide? reflux A) CH CH CH CH OH + HBr 3

2

2

2

B) CH3CH2CH2CH2OH + PBr3 → C) CH CH CH CH OH + NaBr 3

2

2

2

reflux

D) CH3CH2CH2CH2OH + Br2 → E) Answers A) and B) only Ans: E Topic: Alcohol Reactions Section: 11.8 and 11.9 Difficulty Level: Medium 90. Which reagent(s) would transform propyl alcohol into propyl bromide?

A) Concd. HBr and heat B) PBr3 C) NaBr/H2O and heat D) More than one of these E) All of these Ans: D

233

Topic: General Section: 11.10 Difficulty Level: Easy 91. Which compound is a tosylate?

O CH3

O

S O CH3

Br

O

O

S O CH2 CH3

CH3

S O CH3

O

I

II

III

O CH3

O

S CH3

CH3

O

S O

IV

V

A) I B) II C) III D) IV E) V Ans: A

234

CH3

Topic: Alcohol Reactions Section: 11.10 Difficulty Level: Hard 92. What would be the major product of the following reaction sequence?

H

H H

H

I

OH CH3

I CH3

CH3SO2Cl base I

H

H CH3

II

mesylate

H

I

III

A) I B) II C) III D) IV E) An equimolar mixture of I and II Ans: B

235

I CH3

NaI

?

ethanol H

H

IV

OSO2I CH3

Topic: Alcohol Reactions Section: 11.10 Difficulty Level: Hard 93. What would be the major product of the following reaction sequence?

OH H

CH3SO2Cl

NaI

mesylate

base

?

ethanol

CH3 H

H

I I

CH3

SO2I

CH3

H

II

H I

CH3

H

I

H H

CH3

I

III

H

IV

A) I B) II C) III D) IV E) An equimolar mixture of I and II Ans: A

236

Topic: Alcohol Reactions Section: 11.10 Difficulty Level: Hard 94. What would be the major product of the following reaction sequence?

OH H

pCH3C6H4SO2Cl

NaI

tosylate

base

?

ethanol

CH3 H

I

CH3

II

SO2C6H4CH3

CH3

CH3 H

H I

I

H

I

H

H H

CH3

I

III

A) I B) II C) III D) IV E) An equimolar mixture of I and II Ans: B

237

H

IV

Topic: Alcohol Reactions Section: 11.10 Difficulty Level: Hard 95. What would be the major product of the following reaction sequence?

OH H

pCH3C6H4SO2Cl base

NaBr

tosylate

?

ethanol

CH3 H

Br

H

SO2C6H4CH3

CH3

H

II

H Br

CH3

CH3 Br

I

H H

Br

CH3

H

III

A) I B) II C) III D) IV E) An equimolar mixture of II and III Ans: C

238

H

IV

Topic: Alcohol Reactions Section: 11.10 Difficulty Level: Hard 96. What would be the major product of the following reaction sequence?

OH H

pCH3C6H4SO2Cl base

NaOH

tosylate

?

H2O

CH3 H

H

OH OH

CH3

SO2C6H4CH3

CH3

H

II

H OH

CH3

H

I

H H

CH3

OH

III

H

IV

A) I B) II C) III D) IV E) An equimolar mixture of I and II Ans: A Topic: Alcohol Reactions Section: 11.10 Difficulty Level: Hard 97. cis-3-Methylcyclopentanol is treated with CH3SO2Cl in the presence of a base. The product of the reaction then is allowed to react with KI in methanol. What is the final product?

A) trans-1-Iodo-3-methylcyclopentane B) cis-1-Iodo-3-methylcyclopentane C) 1-Methylcyclopentene D) 2-Methylcyclopentene E) 3-Methylcyclopentene Ans: A

239

Topic: Alcohol Reactions Section: 11.10 Difficulty Level: Hard 98. The major product of the following reaction would be: CH3 H

OH

CH3SO2Cl

Product

base

CH3CO2-

?

C2H5

CH3 H3CCO2

CH3

CH3 H

H

O2CCH3

C2H5

C2H5

I

II

H3CCO2

OSO2CH3

C2H5

III

A) I B) II C) III D) Equal amounts of I and II E) None of these Ans: A Topic: Alcohol Reactions Section: 11.10 Difficulty Level: Hard 99. trans-3-Methylcyclopentanol is treated with CH3SO2Cl in the presence of base. The product of this reaction is then heated with KI in methanol. What is the final product?

A) trans-1-Iodo-3-methylcyclopentane B) cis-1-Iodo-3-methylcyclopentane C) 1-Methylcyclopentene D) 2-Methylcyclopentene E) 3-Methylcyclopentene Ans: B

240

Topic: Alcohol Reactions/Stereochemistry Section: 11.10 Difficulty Level: Hard O

100.

CH3

S

OH,

O Methanesulfonic acid, is treated, in turn, with PCl5 and (R)-2-butanol.

Which of the following Fischer formulas is a stereochemically correct representation of the final product?

H

CH3 MsO

MsO

H

O CH3

H3C

CH2CH3

CH2CH3

II

I

O H3C

O CH3

O

S

H

O

CH2CH3

III

H

S

CH3

H3C

CH2CH3

CH3

S

Cl

O

CH2CH3

V

IV

A) I B) II C) III D) IV E) V Ans: A

241

Topic: Reaction Mechanisms Section: 11.11 Difficulty Level: Medium 101. The following reaction, 2 CH3CH2CH2CH2OH

H2SO4

(CH3CH2CH2CH2)2O

heat

+

H2O

is probably: A) an SN1-type reaction involving the protonated alcohol as the substrate.

B) an SN2-type reaction involving the protonated alcohol as the substrate.

C) an E1-type reaction involving the protonated alcohol as the substrate.

D) an E2-type reaction involving the protonated alcohol as the substrate.

E) an epoxidation reaction.

Ans: B Topic: Ether Synthesis Section: 11.11B Difficulty Level: Medium 102. Which is the best way to prepare 3-methoxypentane via the Williamson method?

A) CH3OH + CH3CH2CHOHCH2CH3 + H2SO4, 140°C B) CH3OH + (CH3)2CHCH2CH2OH + H2SO4, 140°C C) CH3ONa + (CH3CH2)2CHBr D) CH3I + (CH3CH2)2CHONa E) CH3I + (CH3)2CHCH2CH2ONa Ans: D Topic: Ether Synthesis Section: 11.11B Difficulty Level: Medium 103. Which method would provide the best synthesis of ethyl isopropyl ether?

A) (CH3)2CHONa + CH3CH2Br → B) CH3CH2ONa + (CH3)2CHBr → C) H2SO4, 140 oC CH3CH2OH + (CH3)2CHOH D) H2SO4, 180 oC CH3CH2OH + (CH3)2CHOH E) CH3CH2ONa + (CH3)2CHOH → Ans: A

242

Topic: Ether Synthesis Section: 11.11B Difficulty Level: Medium 104. Which is the best method for the synthesis of tert-butyl methyl ether?

A) CH3ONa + (CH3)3CBr → B) (CH3)3CONa + CH3I → C) CH3OH + (CH3)3COH + H2SO4 at 140° C → D) (CH3)3CONa + CH3OCH3 → E) CH3ONa + (CH3)3COH → Ans: B Topic: Ether Synthesis Section: 11.11B Difficulty Level: Hard 105. Which is the best method to prepare 2-ethoxy-5-methylhexane?

A) C2H5ONa + (CH3)2CHCH2CH2Br B) C2H5ONa + (CH3)2CHCH2CH2CH2CH2Br C) C2H5ONa + (CH3)2CHCH2CH2CHBrCH3 D) C2H5Br + (CH3)2CHCH2CH2CH(CH3)ONa E) C2H5OH + (CH3)2CHCH2CH2CHOHCH3 + H2SO4, 140°C Ans: D Topic: Ether Synthesis Section: 11.11C Difficulty Level: Hard 106. When 3-methyl-2-pentene is treated with mercuric acetate, Hg(O2CCH3)2, in a THFethanol mixture and the resulting product reacted with NaBH4 in basic solution, the principal product formed is which of these?

A) 3-methyl-3-pentanol B) 3-ethoxy-3-methylpentane C) 3-methyl-2-pentanol D) 2-ethoxy-3-methylpentane E) 1-ethoxy-3-methylpentane Ans: B

243

Topic: Ether Synthesis Section: 11.11C Difficulty Level: Hard 107. When 3-methyl-2-pentene is treated with mercuric acetate, Hg(O2CCH3)2, in a THF-tbutyl alcohol mixture and the resulting product reacted with NaBH4 in basic solution, the principal product formed is which of these?

A) 3-methyl-3-pentanol B) 3-t-butoxy-3-methylpentane C) 3-methyl-2-pentanol D) 2- t-butoxy -3-methylpentane E) 1- t-butoxy -3-methylpentane Ans: B Topic: Alcohol Reactions Section: 11.11E Difficulty Level: Medium 108. What is the product of the reaction of propyl alcohol with (CH3)3SiCl in the presence of a tertiary amine?

A) CH3CH2CH2Si(CH3)3 B) (CH3)2CHSi(CH3)3 C) CH3CH2CH2OSi(CH3)3 D) (CH3)2CHOSi(CH3)3 E) (CH3CH2CH2)3SiOH Ans: C

244

Topic: Ether Reaction Rates Section: 11.12 Difficulty Level: Easy 109. Which of these ethers is least likely to undergo significant cleavage by hot aqueous H2SO4 ?

CH3OCH3

CH3OCH(CH3)2

(CH3)2CHOCH(CH3)2

I

II

III

(CH3)3COC(CH3)3

O

IV

V

A) I B) II C) III D) IV E) V Ans: A Topic: Chemical Tests Section: 11.12 Difficulty Level: Medium 110. Which of the reagents listed below would serve as the basis for a simple chemical test to distinguish between and

?

O

A) AgNO3 in alcohol B) NaOH in H2O C) Br2 in CCl4 D) Cold concd. H2SO4 E) KMnO4 in H2O Ans: D

245

Topic: Chemical Tests Section: 11.12 Difficulty Level: Medium 111. Which of the reagents listed below would serve as the basis for a simple chemical test to distinguish between and

Br

O

?

A) AgNO3 in C2H5OH B) Dilute HCl C) Br2 in CCl4 D) NaOH in H2O E) KMnO4 in H2O Ans: A Topic: Ether Reactions Section: 11.12A Difficulty Level: Medium 112. The product(s) of the following reaction

excess HBr

is/are:

heat O

O

and

OH

Br

II

I

Br Br OH

and

Br Br O

III

IV

A) I B) II C) III D) IV E) None of these Ans: C

246

Topic: Ether Reactions Section: 11.12A Difficulty Level: Medium 113. The product(s) of the following reaction excess HI

is/are:

heat O

O

and

OH

I

II

I

I I OH

and

I I O

III

IV

A) I B) II C) III D) IV E) None of these Ans: C

247

Topic: Ether Reactions Section: 11.12A Difficulty Level: Medium 114. The product(s) of the following reaction 1 equiv. HI

is/are:

heat O

O

OH

and

I

II

I

I I OH O

III

IV

A) I B) II C) III D) IV E) None of these Ans: C

248

Topic: Ether Reactions Section: 11.12A Difficulty Level: Medium 115. The product(s) of the following reaction 1 equiv. HI

is/are:

heat O

I OH

O

I

II I

I OH

III

O

IV

A) I B) II C) III D) IV E) None of these Ans: B

249

Topic: Ether Reactions Section: 11.12A Difficulty Level: Medium 116. The product(s) of the following reaction 1 equiv. HI

is/are:

heat O

I OH

O

I

II I

I OH

III

O

IV

A) I B) II C) III D) IV E) None of these Ans: C

250

Topic: Ether Reactions, Mechanisms Section: 11.12A Difficulty Level: Medium 117. Select the potential energy diagram that best represents the following reaction: OCH3

I

HI

+

A) I B) II C) III D) IV E) V Ans: E

251

CH3OH

Topic: Ether Reactions, Mechanisms Section: 11.12A Difficulty Level: Medium 118. Assuming an overall exothermic process, select the potential energy diagram that best represents the following reaction: HI O

OH

A) I B) II C) III D) IV E) V Ans: A

252

+

CH3I

Topic: Ether Reactions Section: 11.12A Difficulty Level: Medium 119. What would be the major product(s) of the following reaction Concd. HBr (xs)

C6H5CH2OCH3

heat

?

A) C6H5Br + CH3OH B) C6H5CH2Br + CH3Br C) C6H5CH2OH + CH3Br D) C6H5CH2Br + CH3OH E) C6H5CH2CH2Br Ans: B Topic: Ether Reactions Section: 11.12A Difficulty Level: Medium 120. What would be the major product(s) of the following reaction O

1 equiv. HBr(conc) heat

A) C6H5Br + CH3OH B) C6H5CH2Br + CH3Br C) C6H5CH2OH + CH3Br D) C6H5CH2Br + CH3OH E) C6H5CH2CH2Br Ans: D

253

?

Topic: Epoxide Synthesis Section: 11.13 Difficulty Level: Medium 121. If cis-2-butene is treated with meta-chloroperbenzoic acid what is the final product?

H

H

H3C

I

CH3

H

CH3

H3C

O

O

O

O

H3C

H

H3C

H

H H3CH2C

H

III

II

H H

IV

A) I B) II C) III D) IV E) None of the above Ans: A Topic: Epoxide Synthesis Section: 11.13 Difficulty Level: Medium 122. If trans-2-butene is treated with meta-chloroperbenzoic acid what is the final product?

H

H

H3C

I

CH3

H

CH3

H3C

O

O

O

O

H

H3C

H

H3C

H

III

II

A) I B) II C) III D) IV E) None of the above Ans: B

254

H H3CH2C

H H

IV

Topic: Epoxide Synthesis Section: 11.13 Difficulty Level: Medium 123. If (Z)-2-pentene is treated with meta-chloroperbenzoic acid what is the final product?

H

H

H

CH3 H3CH2C

H3CH2C

O

O

O

I

H3C

CH3

H

H3CH2C

H

H

III

II

A) I B) II C) III D) All of the above E) None of the above Ans: A Topic: Epoxide Synthesis Section: 11.13 Difficulty Level: Medium 124. If (E)-2-pentene is treated with meta-chloroperbenzoic acid what is the final product?

H

H

H

CH3 H3CH2C

H3CH2C

O

O

O

I

H3C

CH3 H

H

H3CH2C

H

III

II

A) I B) II C) III D) All of the above E) None of the above Ans: B

255

Topic: Epoxide Reactions, Isotope Labeling Section: 11.14 Difficulty Level: Medium 125. Select the structure of the major product formed in the following reaction.

HA CH3CH CH2 ?

18 O H2 O 18 A) CH3CH2CH2 OH B) CH3CHCH3 18OH

C) CH3CHCH2OH 18OH

D) CH3CH E)

CH2

OH 18OH CH3CHCH218OH 18OH

Ans: C Topic: Ether Reactions Section: 11.14 Difficulty Level: Medium 126. Heating 2-ethoxyhexane with excess concentrated HBr would produce: A) CH3CH2OCH2CH2CH2CH2CH2CH2Br B) BrCH2CH2OCH2CH2CH2CH2CH2CH3 C) CH3CH2OH and CH3CH2CH2CH2CHBrCH3 D) CH3CH2Br and CH3CH2CH(OH)CH2CH2CH3 E) CH3CH2Br and CH3CH2CH2CH2CHBrCH3 Ans: E

256

Topic: Ether Reactions Section: 11.14 Difficulty Level: Medium 127. Heating 2-ethoxyhexane with one equivalent of concentrated HBr would produce: A) CH3CH2OCH2CH2CH2CH2CH2CH2Br B) BrCH2CH2OCH2CH2CH2CH2CH2CH3 C) CH3CH2OH and CH3CH2CH2CH2CHBrCH3 D) CH3CH2Br and CH3CH2CH(OH)CH2CH2CH3 E) CH3CH2Br and CH3CH2CH2CH2CH(OH)CH3 Ans: E Topic: Ether Reactions Section: 11.14 Difficulty Level: Medium 128. Heating 2-ethoxyhexane with one equivalent of concentrated HI would produce: A) CH3CH2OCH2CH2CH2CH2CH2CH2I B) ICH2CH2OCH2CH2CH2CH2CH2CH3 C) CH3CH2OH and CH3CH2CH2CH2CHICH3 D) CH3CH2I and CH3CH2CH(OH)CH2CH2CH3 E) CH3CH2I and CH3CH2CH2CH2CH(OH)CH3 Ans: E Topic: Epoxide Reactions Section: 11.14 Difficulty Level: Medium 129. Epoxidation followed by reaction with aqueous base converts cyclopentene into which of these?

H OH

I

H

H

H

OH

OH OH

H

II

III

OH

OH H H OH

IV

A) I B) II C) III D) IV E) Equal amounts of III and IV Ans: E

257

Topic: Epoxide Reactions Section: 11.14 Difficulty Level: Medium 130. What would be the major product of the following reaction sequence?

O

H3O+

CH3O-

?

CH3OH

OH

I

II

OH

OCH3 OH

OCH3 OCH 3

OCH3

OH

IV

III

A) I B) II C) III D) IV E) Equal amounts of II and IV Ans A Topic: Epoxide Reactions Section: 11.14 Difficulty Level: Medium 131. What would be the major product of the following reaction sequence?

O

H+

?

CH3OH

OH

I

II

OH

OCH3 OH

OCH3 OCH 3

OCH3

IV

III

A) I B) II C) III D) IV E) Equal amounts of II and IV Ans C

258

OH

Topic: Epoxide Synthesis/Reactions Section: 11.13 and 11.14 Difficulty Level: Hard 132. cis-3-Hexene is treated with meta-chloroperbenzoic acid and the product is then subjected to acid-catalyzed hydrolysis. What is the final product?

CH2CH3 H H H

OH CH2CH3

CH2CH3 H H H HO CH2CH3

CH2CH3 CH2CH3 OH H H HO H OH HO H CH2CH3 CH2CH3

II I A) equal amounts I and II B) equal amounts I, II and V C) equal amounts III, IV and V D) equal amounts III and IV E) Only V Ans: D

III

CH2CH3 OH H H

IV

OH CH2CH3

V

Topic: Epoxide Synthesis/Reactions Section: 11.13 and 11.14 Difficulty Level: Hard 133. trans-3-Hexene is treated with meta-chloroperbenzoic acid and the product is then subjected to acid-catalyzed hydrolysis. What is the final product?

CH2CH3 H H H

OH CH2CH3

CH2CH3 H H H HO CH2CH3

CH2CH3 CH2CH3 OH H H HO H OH HO H CH2CH3 CH2CH3

II I A) equal amounts I and II B) equal amounts I, II and V C) equal amounts III, IV and V D) equal amounts, III and IV E) Only V Ans: E

III

IV

259

CH2CH3 OH H H

OH CH2CH3

V

Topic: Epoxide Synthesis and Reactions Section: 11.13A and 11.14 Difficulty Level: Medium 134. What would be the final product?

O

CH3

RCOOH

CH2

H3CC

product

CH3OH, HA

final product

A) (CH3)2CHCH2OCH3 B) (CH3)2CCH3 OCH3

C) (CH3)2CCH2OH OCH3

D) (CH3)2CCH2OCH3 OH

E) (CH3)2CCH2OCH3 OCH3

Ans: C Topic: Epoxide Synthesis/Reactions Section: 11.13A and 11.14 Difficulty Level: Medium 135. What would be the major product of the following reaction sequence?

RCOOOH

OH

O

I

NH3

OH

II

?

OH

NH2

NH2

IV

III

A) I B) II C) III D) IV E) Equal amounts of II and IV Ans C

260

OH

Topic: Epoxide Reactions Section: 11.15 Difficulty Level: Hard 136. Which compound (or compounds) would be produced when trans-2-butene is treated first with a peroxy acid to form an epoxide, and then the epoxide is subjected to acidcatalyzed hydrolysis?

H HO

CH3 CH3

HO

CH3 H

H

OH

C

C

C

C

C

C

H

CH3 OH

HO

CH3 H

H3C

H OH

I II A) An equimolar mixture of I and II B) An equimolar mixture of II and III C) I alone D) II alone E) III alone Ans: E

III

261

Topic: Epoxide Reactions Section: 11.15 Difficulty Level: Hard 137. Which compound (or compounds) would be produced when cis-2-butene is treated first with a peroxy acid to form an epoxide, and then the epoxide is subjected to acidcatalyzed hydrolysis?

H

CH3

HO

CH3

HO

CH3 H

H

OH

C

C

C

C

C

C

H

CH3

HO

OH

CH3 H

H3C

H OH

I II A) An equimolar mixture of I and II B) An equimolar mixture of II and III C) I alone D) II alone E) III alone Ans: A

III

Topic: Nomenclature Section: 11.16 Difficulty Level: Hard 138. What is the correct IUPAC name for the following compound?

O O O O O

A) 15-crown-5 B) 15-crown-4 C) 5-crown-15 D) 15-crown-15 E) Cyclopentadecane pentaether Ans: A

262

Topic: Nomenclature Section: 11.16 Difficulty Level: Hard 139. What is the correct IUPAC name for the following compound?

O

O

O O

A) 12-crown-5 B) 12-crown-4 C) 4-crown-12 D) 12-crown-12 E) Cyclododecane tetraether Ans: B

SHORT ANSWER QUESTIONS Topic: Isomers Section: 11.1A Difficulty Level: Medium 140. Draw all of the primary alcohols corresponding to the formula C5H12O, including stereoisomers.

Ans: H OH

OH

H OH

OH

OH

263

Topic: Isomers Section: 11.1A Difficulty Level: Medium 141. Draw all of the enantiomeric forms corresponding to the formula C5H12O. Ans: H

HO

H OH

HO

H

HO

OH

H

HO

H

Topic: Isomers Section: 11.1A Difficulty Level: Medium 142. Draw all the enantiomeric forms of ethers with the formula C5H12O. Ans: O

O

H

H

Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 143. Give the correct IUPAC name corresponding to the following structure: OH

Ans: (R)-3-ethyl-2-methyl-3-hexanol

264

H

Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 144. Give the correct IUPAC name corresponding to the following structure: Br

H

CH3 OH

Ans: (1R,2R)-2-bromo-1-methylcyclopentanol Topic: Nomenclature Section: 11.1A Difficulty Level: Hard 145. Give the correct IUPAC name corresponding to the following structure:

OH

Ans: 6-cyclohexyl-2,7-dimethyl-3-octanol Topic: Isomerism Section: 11.1B Difficulty Level: Easy 146. Draw structures for all possible ethers having the formula C4H10O O Ans: O O C4H10O: ethers Topic: Isomers Section: 11.1B Difficulty Level: Medium 147. Draw all of the ethers corresponding to the formula C5H12O, including stereoisomers.

Ans: O

O O

O

O

O

O

H

H

265

Topic: Nomenclature Section: 11.1B Difficulty Level: Hard 148. Give the correct IUPAC name corresponding to the following structure:

O

O

Ans: 1,3-diethoxyhexane Topic: Ether Reactivity Section: 11.3D Difficulty Level: Easy 149. Long-term storage of ethers can be dangerous, because most ethers react slowly with oxygen by a radical process called __________________. This process forms peroxides and hydroperoxides which are dangerously _______________.

Ans: autooxidation, explosive Topic: General, Alcohol Synthesis Section: 11.4 Difficulty Level: Easy 150. We have learned three different methods to convert alkenes into alcohols. a. The method that takes place with Markovnikov regioselectivity but is prone to rearrangement is ________________. b. The method that takes place with Markovnikov regioselectivity and does not lead to rearrangement is _____________. c. The method that takes place with anti-Markovnikov regioselectivity and syn stereoselectivity is _______________.

Ans: a. acid-catalyzed hydration; b. oxymercuration-demercuration; c. hydroborationoxidation

266

Topic: Alcohol Synthesis/Mechanism Section: 11.4 Difficulty Level: Medium 151. What reaction is needed to accomplish the following transformation: H3O+

OH

Ans: Oxymercuration/demurcuration Topic: Alcohol Synthesis/Mechanism Section: 11.4 Difficulty Level: Hard 152. Propose a mechanism for the following transformation: OH

H3O+

Ans: H2 O

H+ H OH

OH

-H+

267

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Hard 153. Draw the structures of all the products formed when (3R)-3-methylcyclopentene is subjected to the hydroboration-oxidation sequence.

Ans: The alkene is symmetrically substituted: thus, Markovnikov rule does not apply.

Hence, all four products shown below are likely to be formed in roughly equal proportions.

H3C

H

hydroboration-oxidation (3R)-3-methylcyclopentene H3C

H3C

H

H3C

H

H3C

H

H

OH

OH

+

+

+ OH

OH

Topic: Alcohol Synthesis Section: 11.4 Difficulty Level: Hard 154. Draw the products formed from the oxymercuration-demercuration of 3methylcyclopentene.

Ans:

OH

and

OH

268

Topic: General, Alcohol Reactions Section: 11.5 Difficulty Level: Easy 155. Reactions of alcohols can be broadly categorized into three types. a. Those that utilize the hydroxyl oxygen as a ____________. b. Those that utilize the hydroxyl proton as an _________. c. Those that convert the hydroxyl group into a _____________.

Ans: nucleophile or base; b. acid; c. leaving group Topic: Alcohol as Acids Section: 11.6 Difficulty Level: Easy 156. Finish the following acid-base reaction and predict if it will proceed in the forward direction: OH

+ NaNH2

OH

+ NaNH2

Ans: Yes ONa

+

NH3 pKa = 35

pKa = 18

Topic: Alcohol as Acids Section: 11.6 Difficulty Level: Easy 157. Finish the following acid-base reaction and predict if it will proceed in the forward direction: OH

+

Na+ C

+

+

CH

Ans: Yes OH

Na C

ONa

CH

+ HC

CH

pKa = 25 pKa = 18

269

Topic: Alcohol as Acids Section: 11.6 Difficulty Level: Easy 158. Finish the following acid-base reaction and predict if it will proceed in the forward direction: +

OH

CH3COONa

Ans: OH

+

CH3COONa

No

ONa

+

CH3COOH pKa = 5

pKa = 18

Topic: General Section: 11.9 Difficulty Level: Medium 159. When an alcohol in which the OH is attached to a stereogenic carbon reacts with thionyl chloride (SOCl2) in the presence of a 3° amine, the resulting alkyl chloride is produced with _____________ of configuration.

Ans: inversion Topic: General Section: 11.10 Difficulty Level: Easy 160. Stereochemically speaking, conversion of an alcohol into a tosylate occurs with _____________ of configuration.

Ans: retention

270

Topic: Multistep Reactions Section: 11.10 Difficulty Level: Medium 161. Complete the following reaction sequence, giving structures for compounds C and D: CH3SO2Cl DMF

OH

C

CH3OH

D

Na2CO3

Ans:

C

=

D

=

=

OMs

OCH3

Topic: Multistep Reactions Section: 11.10 Difficulty Level: Medium 162. Supply the missing reagents A and B. OH

CN

OTs

B

A

CH3

Ans: A pCH3C6H4SO2Cl, base

CH3

CH3

B NaCN in ehtanol

Topic: General Section: 11.11B Difficulty Level: Easy 163. The SN2 reaction between an alkoxide and an alkyl halide is commonly referred to as the _________________ synthesis.

Ans: Williamson Topic: Ether Synthesis Section: 11.11B Difficulty Level: Easy 164. Which is the most efficient way to prepare isopropyl methyl ether via the Williamson method?

Ans: CH3I + (CH3)2CHONa

271

Topic: Ether Synthesis/Mechanism Section: 11.11B Difficulty Level: Medium 165. Propose a mechanism for the following transformation: Br

-

OH

HO

O

Ans: H

Br

O -

Br

O

O

OH

Topic: Ether Synthesis Section: 11.11B Difficulty Level: Medium 166. Predict the product of the following reaction: Br HO

-

OH

Ans:

O

272

Topic: Ether Synthesis/Mechanism Section: 11.11B Difficulty Level: Medium 167. Propose a mechanism for the following transformation: HO

Br

-

OH O

Ans:

O

H

O

Br

Br O

-

OH

Topic: Ether Synthesis/Mechanism Section: 11.11B Difficulty Level: Medium 168. Propose a mechanism for the following transformation: Br HO

-

OH O

Ans: Br H

O

Br O O

-

OH

273

Topic: Ether Synthesis/Mechanism Section: 11.11B Difficulty Level: Medium 169. Propose a mechanism for the following transformation: OH

OH O

Br

Ans: H

OH

O

O O

Br

Br

Topic: Ether Synthesis Section: 11.11B Difficulty Level: Medium 170. Which is the best method to prepare ethoxycyclopentane via the Williamson method?

Ans: O ONa + I

274

Topic: Ether Synthesis/Mechanism Section: 11.11B Difficulty Level: Medium 171. Propose a mechanism for the following transformation: O

I

1 equiv. HI

+

CH3OH

heat

Ans: O

O H

I

H

CH2 I -

I -CH3OH

Topic: Multistep Reactions Section: 11.6 and 11.11B Difficulty Level: Medium 172. Complete the following reaction sequence, giving structures for compounds A and B: Nao OH

DMF

CH3Br

A

B

-H2

Ans:

A

=

=

B

=

ONa

OCH3

275

Topic: Multistep Reactions Section: 11.11C Difficulty Level: Medium 173. Supply the missing reagents A and B. OC(CH3)3

B

A

Ans:

A = Hg(OAc)2, THF, HOC(CH3)3

B = NaBH4

Topic: General Section: 11.13 Difficulty Level: Easy 174. Three-membered rings containing oxygen are called _______________ or ______________.

Ans: oxiranes; epoxides Topic: General Section: 11.13B Difficulty Level: Medium 175. A reaction which leads to a product of particular stereoisomeric outcome, depending on the stereochemistry of the reactant, is termed_________________.

Ans: stereospecific Topic: Epoxide Synthesis and Reactions Section: 11.13 and 11.14 Difficulty Level: Hard 176. Provide a reasonable synthetic strategy for the synthesis of trans-1,2cyclohexanediol from bromocyclohexane Ans Br : CH3ONa

m-CPBA O

CH3OH

OH

+

H3O

OH

+ enantiomer

276

Topic: Epoxide Synthesis and Reactions Section: 11.13 and 11.14 Difficulty Level: Hard 177. Provide a reasonable synthetic strategy for the synthesis of trans-2methoxycyclopentanol from bromocyclopentane Ans: OH

Br O

CH3ONa

m-CPBA

CH3ONa

OCH3

CH3OH

CH3OH

+ enantiomer

Topic: General Section: 11.16 Difficulty Level: Medium 178. The development of a procedure called __________________ has made the use of nonpolar solvents possible in reactions involving polar reagents.

Ans: phase transfer catalysis Topic: General Section: 11.16 Difficulty Level: Medium 179. The relationship between a crown ether and the ion it transports is known as the ____________________ relationship.

Ans: guest-host Topic: General Section: 11.16 Difficulty Level: Medium 180. A compound or ion that prefers a nonpolar environment to an aqueous one is said to be ______________.

Ans: lipophilic

277

Topic: Spectroscopy of Alcohols Section: Various Difficulty Level: Medium 181. Propose a structure for the compound with the following formula that is consistent with the IR and 1H NMR data shown: C3H8O IR – 3350cm−1, strong, broad 6H doublet at 1.3 δ, J = 7 Hz 1H singlet at 2.2 δ, (exchangeable) 1H septet at 4.0 δ, J = 7 Hz Ans: OH

Topic: Spectroscopy of Ethers Section: Various Difficulty Level: Medium 182. Propose a structure for the compound with the following formula that is consistent with the IR and 1H NMR data shown: C4H10O IR – 1125cm−1, strong, broad 6H triplet at 1.2 δ, J = 7 Hz 4H quartet at 3.7 δ, J = 7 Hz Ans: O

278

Topic: Spectroscopy of Ethers Section: Various Difficulty Level: Medium 183. Propose a structure for the compound with the following formula that is consistent with the IR and 1H NMR data shown: C6H14O IR – 1120cm−1, strong, broad 6H triplet at 0.9 δ 4H sextet at 1.5 δ 4H triplet at 3.4 δ Ans: O

Topic: Spectroscopy of Alcohols Section: Various Difficulty Level: Medium 184. Propose a structure for the compound with the following formula that is consistent with the IR and 1H NMR data shown: C7H8O IR – 3325cm−1, strong, broad 1H broad singlet at 2.3 δ (exchangeable) 2H singlet at 4.6 δ 5H multiplet at 7.3 δ Ans: OH

279

Topic: Multistep Synthetic Strategy Section: Various Difficulty Level: Hard 185. Provide a reasonable synthetic strategy for the synthesis of a racemic mixture of (1R,2R) and (1S,2S)-2-bromo-1-methylcyclopentanol from methylcyclopentane: CH3 Ans: CH3 Br2 CH3 CH3ONa Br CH3OH hν heat Br2, H2O Br

H

CH3 OH

Br

+

H

CH3 OH

(1R,2R) (1S,2S) 2-bromo-1-methylcyclopentanol Topic: Multistep Synthetic Strategy Section: Various Difficulty Level: Hard 186. Provide a reasonable synthetic strategy for the synthesis of a racemic mixture of (1R,2R) and (1S,2S)-2-bromo-1-methylcyclopentanol from methylenecyclopentane: Br Ans: HBr

Br

H

+ enantiomer OH

280

NaOCH3

Br2

HOCH3

H2 O

Topic: Multistep Reactions Section: Various Difficulty Level: Hard 187. Complete the following reaction sequence, giving structural details of all key intermediates: i) Li, NH3 ? ii) KMnO4 ,OH−, H2O iii) H3O+ Ans: Li NH3 i) KMnO4 ,OH−, H2O ii) H3O+ H

HO

OH

H

+ H

OH

HO

(2S,3S)-pentane-2,3-diol

281

H

(2R,3R)-pentane-2,3-diol

Topic: Multistep Reactions Section: Various Difficulty Level: Hard 188. Complete the following reaction sequence, giving structural details of all key intermediates: i) P-2, H2 ? ii) KMnO4 ,OH−, H2O iii) H3O+ P-2, H2

i) KMnO4 ,OH−, H2O ii) H3O+ H

HO

OH

H

+ HO

Ans:

H

H

(2S,3R)-pentane-2,3-diol

OH

(2R,3S)-pentane-2,3-diol

Topic: Multistep Reactions Section: Various Difficulty Level: Hard 189. Complete the following reaction sequence, giving structural details of all key intermediates: i) Lindlar catalyst, H2 ? ii) KMnO4 ,OH−, H2O iii) H3O+ Ans: Lindlar catalyst H2 i) KMnO4 ,OH−, H2O ii) H3O+ H

HO

OH

H

+ HO

H

(2S,3R)-pentane-2,3-diol

H

OH

(2R,3S)-pentane-2,3-diol

282

Topic: Multistep Reactions Section: Various Difficulty Level: Hard 190. Complete the following reaction sequence, giving structural details of all key intermediates: i) Lindlar catalyst, H2 ? ii) OsO4 iii) NaHSO3 i) Lindlar catalyst H2 ii) OsO4 iii) NaHSO3 H

HO

OH

H

+ HO

H

(2S,3R)-pentane-2,3-diol

H

OH

(2R,3S)-pentane-2,3-diol

Topic: Multistep Reactions Section: Various Difficulty Level: Hard 191. Complete the following reaction sequence, giving structural details of all key intermediates: i) H2, Lindlar catalyst ? ii) KMnO4 ,OH−, H2O iii) H3O+ Ans: H2 Lindlar catalyst

−

H

OH

i) KMnO4 ,OH , H2O ii) H3O+

HO

H

meso

283

Topic: Multistep Reactions Section: Various Difficulty Level: Hard 192. Complete the following reaction sequence, giving structural details of all key intermediates: i) H2, P-2 ? ii) KMnO4 ,OH−, H2O iii) H3O+ Ans:

H

OH

−

H2, P-2

i) KMnO4 ,OH , H2O ii) H3O+

HO

H

meso

Topic: Multistep Reactions Section: Various Difficulty Level: Hard 193. Complete the following reaction sequence, giving structural details of all key intermediates: i) Li, NH3 ? ii) m-CPBA iii) H3O+, H2O Ans: Li NH3 i) m-CPBA ii) H3O+, H2O HO

H

H

OH

+ H

OH

(2R,3S)-pentane-2,3-diol

HO

H

(2S,3R)-pentane-2,3-diol

284

Topic: Spectroscopy of Ethers Section: Various Difficulty Level: Hard 194. Propose a structure for the compound with the following formula that is consistent with the IR and 1H NMR data shown: C6H14O IR – 1120cm−1, strong, broad 3H triplet at 1.1 δ 9H singlet at 1.15 δ 2H quartet at 3.45 δ Ans:

O

285

Topic: Spectroscopy of Ethers Section: Various Difficulty Level: Hard 195. A compound has the formula C5H10, with the 13C and 1H NMR spectral data shown.

Propose structure that fits this data.

13

C NMR Broadband decoupled 13C NMR: 23.5, 26.7, 68.9 δ DEPT-90: no peaks DEPT-135: no positive peaks; negative peaks at 23.5, 26.7, 68.9 δ 1

H NMR 1.7 δ, multiplet (6H) 3.72 δ, triplet (4H) J = 7Hz Ans:

O

286

Topic: Spectroscopy of Alcohols Section: Various Difficulty Level: Hard 196. A compound has the formula C6H14O. The 13C and 1H NMR spectral data for this compound are: 13

C NMR Broadband decoupled 13C NMR: 29.7, 29.8, 46.4, 60.0 δ DEPT-90: no peaks DEPT-135: positive peak at 29.8 δ; negative peaks at 29.7, 60.0 δ 1 H NMR 0.91 δ, singlet (9H) 1.53 δ, triplet (2H) J = 7.3Hz 2.13 δ, broad singlet (exchangeable, 1H) 3.70 δ, triplet (2H) J = 7.3Hz Ans:

OH

287