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Chapter Seven

MULTIPLE CHOICE QUESTIONS


1. The correct IUPAC name for the following compound is:
Br

A)
B)
C)
D)
E)

2-Bromo-4-methylenehexane
2-(2-Bromopropyl)-1-butene
4-Bromo-2-ethyl-1-pentene
2-Bromo-4-ethyl-1-pentene
2-Bromo-4-ethyl-4-pentene
Ans: C

130

2. Name the following compound:

OCH3

A)
B)
C)
D)
E)

(cis)-3-methoxyhex-3-ene
(Z)-4-methoxyhex-4-ene
(Z)-3-methoxyhex-3-ene
(E)-3-methoxyhex-3-ene
3-methoxyhex-3-ene
Ans: C

131

3. Name the following compound:

HO

A) (E)-4-phenyl-4-methylbut-3-en-1-ol
B) (E)-4-phenylpent-3-en-1-ol
C) (Z)-4-phenylpent-3-en-1-ol

132

D) (Z)-4-phenyl-4-methylbut-3-en-1-ol
E) (E)-4-benzylpent-3-en-1-ol
Ans: B

133

4. Which structure represents (Z)-4-bromohexa-1,3-diene?


A)

Br

B)

Br
134

C)

Br
D)

Br

E) None of the above


Ans: C

135

5. Which structure represents (E)-1-bromo-2-methylhex-2-ene?


A)

Br

B)
C)
D)

Br

Br
Br

E) None of the above


Ans: A

136

137

6. Which structure represents (Z)-1,4-dichlorohex-3-en-1-yne?


A)

Cl
Cl
B)

Cl

138

C)

Cl
Cl
D)
E) None of the above
Ans: B

Cl

7. A correct IUPAC name for the following compound is:


A)
B)
C)
D)
E)

3,3,5-trimethyl-2-hexene
3-isobutyl-3-isopropyl-2-propene
3-isobutyl-4-methyl-2-pentene
3-(1-methylethyl)-5-methyl-2-hexene
None of the above
Ans: E

8. The correct IUPAC name for the following compound is:


A)
B)
C)
D)
E)

4,5-Dimethyl-3-propyl-2-hexene
4,5-Dimethyl-3-propyl-1-hexene
3-(2,3-Dimethylpropyl)-1-hexene
2,3-Dimethyl-4-isopropyl-5-hexene
2,3-Dimethyl-4-propyl-5-hexene
Ans: B

Cl

139

9. Select the structure of 4ethyl-2,3-dimethyl-2-heptene.


A)
B)
C)
D)
E)
Ans: B
10. The correct IUPAC name for the following compound is:
Cl

A)
B)
C)
D)
E)

(E)-2-Bromo-3-chloro-5-methyl-2-hexene
Br
(E)-2-Bromo-3-chloro-5-methyl-3-hexene
(Z)-2-Bromo-3-chloro-5-methyl-3-hexene
(Z)-2-Bromo-3-chloro-5-methyl-2-hexene
(E)-2-Methyl-5-bromo-4-chloro-4-hexene
Ans: A

140

11. Name the following compound:

Br

A)
B)
C)
D)
E)

(S,Z)-3-bromo-4-methylhex-2-ene
(S)-3-bromo-4-methylhex-2-ene
(S,Z)-4-bromo-3-methylhex-4-ene
(S,E)-3-bromo-4-methylhex-2-ene
(R,E)-3-bromo-4-methylhex-2-ene
Ans: A

141

12. Name the following compound:

Br
Br
A)
B)
C)
D)
E)

(S,E)-2,4-dibromo-3-methylpent-2-ene
(R,Z)-2,4-dibromo-3-methylpent-2-ene
(R,E)-2,4-dibromo-3-methylpent-3-ene
(S,E)-2,4-dibromo-3-methylpent-3-ene
(R,E)-2,4-dibromo-3-methylpent-2-ene
Ans: E

142

13. Name the following compound:

OH
A)
B)
C)
D)
E)

(R,Z)-5-phenyloct-5-en-3-ol
(R,Z)-5-benzyloct-5-en-3-ol
(R,E)-5-phenyloct-5-en-3-ol
(R,E)-5-benzyloct-5-en-3-ol
(R,E)-5-benzyloct-3-en-6-ol
Ans: B

143

14. Which structure represents (R,Z)-5-methylhept-2-ene?


A)

B)

144

C)

145

D)

E) None of the above


Ans: D

146

15. Name the following compound:

Cl

147

A)
B)
C)
D)
E)

(S,E)-3-chlorohex-4-en-1-yne
(R,E)-3-chlorohex-2-en-5-yne
(S,E)-3-chlorohex-2-en-5-yne
(R,E)-3-chlorohex-4-en-1-yne
(R,E)-3-chloropent-4-en-1-yne
Ans: D

16. Which molecule would have the lowest heat of hydrogenation?


A)
B)
C)
D)
E)

I
II
III
IV
V
Ans: A

II

III

IV

17. Heats of hydrogenation data would be useful in comparing the relative stabilities of
which of the following substances?
A)
B)
C)
D)

I, II, III
III, IV
I
II
III
IV
V
I, II, V
Heats of hydrogenation data would not be a useful way to compare relative stabilities of
any of the substances.
E) All of the above substances could effectively be compared using heats of hydrogenation
data.
Ans: C

18. Which alkene would liberate the most heat per mole when subjected to catalytic
hydrogenation?
A)
B)
C)
D)
E)
Ans: A

148

19. Which alkene is most stable?


A)
B)
C)
D)
E)

I
II
III
IV
V
Ans: A

II

III

IV

20. Concerning the relative stabilities of alkenes, which is a false statement?


A) Unless hydrogenation of the alkenes gives the same alkane, heats of hydrogenation
cannot be used to measure their relative stabilities.
B) In general, the greater the number of alkyl groups attached to the carbon atoms of the
double bond, the greater the stability of the alkene.
C) The greater the quantity of heat liberated on combustion or hydrogenation of an alkene,
the greater its energy content.
D) trans-Cycloalkenes are always more stable than the cis-isomers.
E) Heats of combustion can be used to measure the relative stabilities of isomeric alkenes,
even though their hydrogenation products are not identical.
Ans: D
21. Which product (or products) would be formed in appreciable amount(s) when trans-1bromo-2-methylcyclohexane undergoes dehydrohalogenation upon treatment with
sodium ethoxide in ethanol?
A)
B)
C)
D)
E)

I
I
II
III
IV
More than one of these
Ans: B

II

III

IV

22. Your task is to convert 2-bromobutane to 1-butene in highest yield. Which reagents
would you use?
A) KOH/H2O
B) KOH/CH3OH
C) CH3ONa/CH3OH
D) CH3CH2ONa/CH3CH2OH
E) (CH3)3COK/(CH3)3COH
Ans: E

149

23. What is the major product for the following reaction?

E
OTs
A)
B)
C)
D)
E)

CH3CH2(CH3)C=CHCH3
CH3CH2(CH3)CHCH=CH2
CH3CH2(CH3)CHCH(OCH2CH3)CH3
None of the above
No reaction
Ans: A

150

24. What is the major product for the following reaction?

tCl

151

A)

Ot-Bu
B)
C)

152

D)

E)

Ans: E

153

25. What is the major product for the following reaction?

154

A)

155

B)

156

C)

157

D)

E)
None of the above
Ans: D

158

26. What is the major product for the following reaction?

E
I

159

A)

160

B)

161

C)

162

D)

E) None of the above


Ans: A

163

27.

What is the major product for the following reaction?

Cl

164

A)

165

B)

166

C)

167

D)

168

E)

Ans: A

169

28. What is the major product for the following reaction?

Br

170

A)

171

B)

172

C)

173

D)

174

E)

Ans: E

175

29. What is the major product for the following reaction?

E
Br

176

A)

177

B)

178

C)

179

D)

E) More than one of the above


Ans: C
30. Dehydrohalogenation of tert-pentyl bromide will produce 2-methyl-1-butene as the
chief product when:
A) CH3COONa is employed as the base.
B) KOH/C2H5OH is employed as the base.
C) CH3CH2ONa/CH3CH2OH is employed as the base.
D) (CH3)3COK/(CH3)3COH is employed as the base.
E) any base is used, as long as the temperature is sufficiently high.
Ans: D

180

31. What is the major product for the following reaction?

E
Br

181

A)

OEt
B)
C)

182

D)

E)

Ans: C

183

32. What is the major product for the following reaction?

E
Cl
184

A)

OEt
B)
C)

185

D)

E)

Ans: B

186

33. What is the major product for the following reaction?

1.
OTs
A)
B)

187

2.

C)

D)

188

E)

Ans: C

189

34. What is the major product for the following reaction?

1.
Cl
A)

B)

190

2.

C)

D)

191

E)

Ans: D

192

35. What is the major product for the following reaction?

1.
Cl
A)

B)

193

2.

C)

D)

194

E)

Ans: C

195

36. What is the major product for the following reaction?

1.
Br
A)

B)

196

2.

C)

D)

197

E)

Ans: B

37. Which compound listed below would you expect to be the major product when 2bromo-2-methylbutane is refluxed with KOH/ethanol?
A)
OH
B)
C)
O
D)
E)
Ans: D

198

38. Zaitsev's rule states that:


A) In electrophilic addition of an unsymmetrical reagent to an unsymmetrical alkene, the
more positive portion of the reagent will become attached to the carbon of the double
bond bearing the greater number of hydrogen atoms.
B) An equatorial substituent in cyclohexane results in a more stable conformation than if
that substituent were axial.
C) E2 reactions occur only if the -hydrogen and leaving group can assume an antiperiplanar arrangement.
D) When a reaction forms an alkene, and several possibilities exist, the more (or most)
stable isomer is the one which predominates.
E) The order of reactivity of alcohols in dehydration reactions is 3 > 2 > 1.
Ans: D
39. Regarding the use of potassium tert-butoxide as a base in E2 reactions, it is incorrect to
state that:
A) this base is more effective than ethoxide ion, because it (KO-t-Bu) is the more basic of
the two.
B) it tends to give the anti-Zaitsev, i.e., Hofmann, product.
C) it is more reactive in dimethyl sulfoxide than it is in tert-butyl alcohol.
D) it favors E2 reactions over competing SN2 reactions.
E) it will form, predominantly, the more stable alkene.
Ans: E
40. What is the major product of the reaction,
A)
B)
C)
D)
E)

(CH3)2C=C(CH3)2
(CH3)3CCH=CH2
(CH3)2C=CHCH3
(CH3)2C=CHCH2CH3
None of these
Ans: B

(CH3)3COK
(CH3)3COH
heat

Br

41. Which compound would be the major product?


Br
(CH3)3COK
(CH
) COH
O 3 3
heat

A)
B)
C)
D)
E)

OH

Ans: E

199

42.
A)
B)
C)
D)
E)

Which statement(s) is/are true of acid-catalyzed alcohol dehydrations?


Protonation of the alcohol is a fast step.
Formation of a carbocation from the protonated alcohol is a slow step.
Rearrangements of less stable carbocations to more stable carbocations are common.
Loss of a proton by the carbocation is a fast step.
All of the above
Ans: E

43. Which product(s) would be produced by acid-catalyzed dehydration of 2-methyl-2pentanol?


A)
B)
C)
D)
E)

and
and

Ans: B

44. Which one of the following alcohols would dehydrate most rapidly when treated with
sulfuric acid?
A)
B)
C)
D)
E)

I
II
III
IV
V
Ans: B

OH

OH

OH

II

III
OH

OH

IV

200

45. Which mechanistic step in the acid-catalyzed dehydration of 3,3-dimethyl-2-butanol is


the rate determining step?
A)

Step 1:

+
OH

201

H3O

B)

Step 2:

OH2
C)
D)
E)

Step 3:
Step 4a:
Step 4b:
+ H2O
+ H 2O
Which alcohol would be most easily dehydrated?
CH3
CH3
CH3CH2CCH
CH
CH3 2 3
CH3CH2CHCHCH3
CH3OH
CH3CH2CHCH
2CH2OH
CH2OH
OH
HOCH2CHCH2CH2CH3
Ans: A
CH3CH2CHCH2CH3
Ans: B

46.
A)
B)
C)
D)
E)

202

+
+

H3O+
H3O+

47. Which alcohol would be most easily dehydrated?


A)
B)
C)
D)
E)

I
II
III
IV
V
Ans: B

OH

OH

OH

II

III
OH

OH

IV
V
48. Which alcohol would initially produce the most stable carbocation when treated with
concentrated H2SO4?
A)
OH
B)
C)
D)
OH
HO
E)
HO
OH
Ans: A
49. Carbocations are frequent intermediates in acidic reactions of alkenes, alcohols, etc.
What do carbocations usually do? They may:
A) rearrange to a more stable carbocation.
B) lose a proton to form an alkene.
C) combine with a nucleophile.
D) react with an alkene to form a larger carbocation.
E) do all of the above.
Ans: E
50. Which of the following carbocations would NOT be likely to undergo rearrangement?
CH3CHCHCH3
A)
CH3
B)
CH
3
CH
C)
3
CH3CHCCH
3
CH3 CH
D)
CH3CCH
2
CH3 3
CH
E)
3
CH3CHCH2
Ans: C
CH CCHCH CH
3

CH3

203

51. Neopentyl alcohol, (CH3)3CCH2OH, cannot be dehydrated to an alkene without


rearrangement. What is the chief product of dehydration?

A)
B)
C)
D)
E)

I
II
III
IV
V
Ans: B

II

IV

III

204

52. What is the major product of the reaction between methanol and (2R,3S)-2-bromo-3methylpentane at room temperature?
A)

B)

OCH3

205

C)

D)

H3CO
E) Both A) and C)
Ans: D
53.
A)
B)
C)
D)
E)

Rearrangements are likely to occur in which of the following reaction types?


SN1 reactions
SN2 reactions
E1 reactions
E2 reactions
Both SN1 and E1 reactions
Ans: E

206

54. What is the major product of the reaction of the following reaction?

ethano

207

A)

CH3CH2O

208

B)

OCH2CH3

C)
D)
E) More than one of the above
Ans: A

209

55. What is the major product for the following reaction?

Br

210

A)

211

B)

212

C)

213

D)

E) More than one of the above


Ans: E

214

56. What is the major product for the following reaction?

215

A)

216

B)

217

C)

218

D)

E) None of the above


Ans: C

219

57. What is the major product for the following reaction?

Cl

220

A)

221

B)

222

C)

223

D)

224

E)

Ans: D

225

58. What is the major product of the reaction of the following reaction?

Cl

A)
B)
C)
D)
E)

EtO

OEt

Ans: D

226

59. What is the major product of the reaction of the following reaction?

OTs

227

A)

B)

228

C)

OEt
D)
E) None of the above
Ans: A

229

60. What is the major product of the reaction of the following reaction?

Cl
230

A)

H3CO
B)
C)
D)
E)
Ans: E

231

61. What is the major product of the reaction of the following reaction sequence?

Br

A)

232

B)

C)

233

D)

OEt

E) A mixture of A) and B)
Ans: C
62. Which alkene would you expect to be the major product of the following dehydration?
H2SO4
?

heat

A)
B)
C)
D)
E)

I
II
III
IV
V
Ans: C

OH

III

II

IV

234

63. What will be the major product of the following reaction?


85% H3PO4
?
A)
heat
B)
OH
C)
D)
O
E)
Ans: A

64. Which of the following reactions would yield 3,3-dimethyl-1-butene in a reasonable


percentage yield (i.e., greater than 50%)?
A)
H2SO4
B)
(CH3)3COK,
(CH3)3COH
heat
C)
OH
i) 3 NaNH2heat
, mineral oil, heat
Br
Br
ii) H3O+
D) All of these
Br
E) Answers B) and C) only
Ans: B
65.
A)
B)
C)
D)
E)

Which reaction would yield 2-butyne?


CH3CC:Na + CH3Br
CH3CH2Br + HCC:Na
CH3:Na + HCCCH3
More than one of these
None of these
Ans: A

235

66. Which reaction conditions would not yield 2-butyne from 1-propyne?
A)

a. EtONa, EtOH
b. CH3I
B)

a. CH3Li, THF
b. CH3I
236

C)

a. NaNH2, NH3 (liq


b. CH3I
D)

a. NaCH2CH3, THF
b. CH3I
E) More than one of these
Ans: A

237

67. Which of the following reactions would yield 2-pentyne?


I
A)
NaNH2
B)
Br
(1NaNH
mol) 2
C)
(1 mol)

Br

C
Br
HA
heat
NaOC2H5
OH
Ans: B
C2H5OH
68. Which of the following methods could be used to synthesize 4,4-dimethyl-2-hexyne?
CH3
A)
C2H5 C C C: Na
HCH
B)
3C 3 I
CH
H
C
C
C:
Na
C
H
C
Br ( excess)
C)
3
3
2 5 NaNH
2
CH3
D) More than one of these
NH3 (l)
E) None of these
Br
Br
Ans: D
D)
E)

Br

238

69.
A)
B)
C)

Which statement is/are true about acetylide anions?


They do not alkylate with secondary alkyl halides.
Primary alkyl halides are best suited for alkylation.
In the presence of tertiary alkyl halides, the acetylide anion acts as base to give an
elimination product.
D) Only two of the above are true.
E) All of the statements are true.
Ans: E

239

70. Which reaction would not result in alkylation of the acetylide anion?
A)

Li
B)

Li

240

C)

Li
D)

Li
241

E) None of the above


Ans: C

242

71. Which reaction would not primarily proceed via an SN2 mechanism?
A)

Li
B)

Li

243

C)

Li
D)

Li
244

E) All of them proceed via SN2


Ans: C

245

72. Which would be the major product of the following reaction sequence?

246

A)

CH2CH3
B)

CH=CHT
247

C)

CH=CH2
D)

CH2CH2T
E) None of the above
Ans: D

248

73. An unknown compound, B, has the molecular formula C7H12. On catalytic


hydrogenation 1 mol of B absorbs 2 mol of hydrogen and yields 2-methylhexane. B has
significant IR absorption band at about 3300 and 2200 cm-1. Which compound best
represents B?
A) 3-methyl-1-hexyne
B) 5-methyl-2-hexyne
C) 5-methyl-1,3-hexadiene
D) 5-methyl-1-hexyne
E) 2-methyl-1,5-hexadiene
Ans: D
74. A compound X with the formula C7H10 undergoes catalytic hydrogenation to produce a
compound Y with the formula C7H14. What could be true of X?
A) X might have one triple bond and one ring.
B) X might have two double bonds and one ring.
C) X might have one double bond and two rings.
D) X might have one double bond and one triple bond.
E) More than one of the above
Ans: E
75. A compound, C6H10, which reacts with 2 mol of hydrogen over a platinum catalyst and
which shows an IR absorption band at approximately 3300 cm-1 could be:
A)
B)
C)
D)
E)

I
II
III
IV
V
Ans: C

II

IV

III

76. What is the structure of a compound with formula C6H10 which has IR absorption at
approximately 3300 cm-1 and which can be catalytically reduced with hydrogen to 2methylpentane?
A)
B)
C)
D)
E)
Ans: D

249

77. Upon catalytic hydrogenation, a compound C6H6 absorbs four moles of hydrogen.
Select a structure for C6H6.

I
A)
B)
C)
D)
E)

I, II
III
II, III
IV, V
I, IV, V
Ans: D

78. Given:
One can conclude that X X (C8H14)
has:
A) no rings and no double bonds.
B) no rings and one double bond.
C) one ring and one double bond.
D) two rings and no double bonds.
E) one triple bond.
Ans: C

H2, Pt
25oC

250

Y (C8H16)

79. On hydrogenation, a compound C9H12 absorbs 2 mol of hydrogen. Which of the


following is a possible structure for the compound?

A)
B)
C)
D)
E)

I
II
III
IV
V
Ans: D

III

II

IV

251

80. What is the major product for the following reaction sequence?

Cl
Cl
A)
B)
C)

C
252

D)

E) None of the above


Ans: E

253

81. Which would be the major product of the following reaction sequence?

Cl

Cl
H

A)
B)
C)
D)
E)

(CH3CH2)2C=C=CHT
(CH3CH2)2C=C=CH2
(CH3CH2)2CHCCT
(CH3CH2)2CHCH=CHT
None of the above
Ans: E

254

82. What is the major product for the following reaction sequence?

H
H

1
1

2
A)

255

B)

C)

D)

N
H
E) None of the above
Ans: B

256

83. What is the major product for the following reaction sequence?

1
1

2
A)

257

B)

CH3CH2CH2Br
C)

D)
E) None of the above
Ans: A
84. Which would be the major product of the following reaction?
A)
B)
C)
D)
E)

D2, Ni

I
II
III
IV
V
Ans: A

D CH3

CH3
H CH3

DD

II

III

CH3

DH

CH3

IV

258

85. Which would be the major product of the following reaction sequence?

Br

259

A)

260

B)

C)
D)

D
D
H
D
H
261

E)

D
D
Ans: C

262

86.
A)
B)
C)
D)
E)

Which is not a satisfactory procedure for the synthesis of 3-methyl-1-butene?


(CH3)2CHCCH3 + conc. H2SO4
(CH3)2CHCCH + Li/liq.NH3
(CH3)2CHCH2CH2Br + CH3ONa/CH3OH
(CH3)2CHCHBrCH3 + (CH3)3COK/(CH3)3COH
(CH3)2CHCCH + H2/Ni2B (P-2)
Ans: A

263

87. What is the major product for the following reaction sequence?

Br

Br
A)

264

B)

C)

D)

265

E)

Ans: D

266

88. What is the major product for the following reaction sequence?

Cl
Cl
A)
B)
C)

C
267

D)

E) None of the above


Ans: C

268

89. What is the major product for the following reaction sequence?

H
H

1
1

2
2
A)

269

B)

C)

D)

N
H
E) None of the above
Ans: C

270

90. What is the major product for the following reaction sequence?

H
H

1
1

2
A)

271

B)

C)

D)

N
H
E) None of the above
Ans: C

272

91. What is the major product for the following reaction sequence?

1a. N
1b. C

2a. L
2b. N
A)

273

B)

CH3CH2CH2Br
C)

D)
E) None of the above
Ans: C

274

92. What is the major product for the following reaction sequence?

1
1

2
A)

275

B)

CH3CH2CH2Br
C)

D)
E) None of the above
Ans: D
93.
A)
B)
C)
D)
E)

Which of these is the most satisfactory method for the preparation of cis-2-pentene?
CH3CHBrCH2CH2CH3 + (CH3)3COK/(CH3)3COH
CH3CCCH2CH3 + H2, Pt
CH3CCCH2CH3 + H2, Ni2B (P-2)
CH3CCCH2CH3 + Li/liq. NH3
CH3CH2CHBrCH2CH3 + CH3CH2ONa/CH3CH2OH
Ans: C

94. Which reaction would not be a method for preparing 5-methyl-1-hexyne?


A)
1) NaNH2 (2 mol), liq NH3
B)
Br
+
HC CNa + Cl 2) NH4
C)
D)
CH
NaNH
2 (3 mol), liq NH3
Li + 1)HC
Br
E)
Br
1) NaNH+2 (3 mol), liq NH3
2) NH4
Ans: C
Br
Br
2) NH4+
276

95.
A)
B)
C)
D)
E)

Which of the following reductions of an alkyne is NOT correct?


2-Pentyne + 2H2/Pt pentane
2-Pentyne + H2/Ni2B Z-2-Pentene
2-Pentyne + Li/NH3(l) Z-2-Pentene
All of the above are correct.
None of the above is correct.
Ans: C

96. The structure of the product, C, of the following sequence of reactions would be:
NaNH2
NH3(l)

A)
B)
C)
D)
E)

CH3CH2Br

Br

Ans: A

277

H2
Ni2B [P-2]

97. Which would be the major product of the following reaction sequence?

278

A)

279

B)

280

C)

D
D

281

D)

E) None of the above


Ans: B

282

98. Which would be the major product of the following reaction sequence?

283

A)

D
D

284

B)

285

C)

286

D)

E) None of the above


Ans: A
99. The structure of the product obtained from 2-butyne and Li/C2H5NH2 is:
A)
B)
C)
HN
D)
E)
NH
Ans: A

287

SHORT ANSWER QUESTIONS


100. When an elimination reaction gives the most stable alkene as the major product, we say
that the elimination follows ________________'s rule.
Ans: Zaitsev
Topic: General Information
Section: 7.6C
Difficulty Level: Easy
101. When an elimination reaction gives the less substituted alkene as the major product, we
say that the elimination follows ________________'s rule.
Ans: Hofmann
Topic: General Information
Section: 7.7
Difficulty Level: Easy
102. In a dehydration reaction, the leaving group is _______________.
Ans: a molecule of water
Topic: General Information
Section: 7.7
Difficulty Level: Easy
103. Dehydration of alcohols requires a __________________ catalyst.
Ans: strong acid
Topic: General Information
Section: 7.8
Difficulty Level: Medium

288

104. Carbocations have three options available for further reaction. These options include
reaction with a nucleophile, loss of a beta proton to give an alkene, and
________________.
Ans: rearrangement

Topic: General Information


Section: 7.10
Difficulty Level: Medium
105. Alkynes can be produced from either __________________ or _________________
dihalides.
Ans: vicinal/geminal
Topic: General Information
Section: 7.14
Difficulty Level: Easy
106. In hydrogenation reactions, both hydrogen atoms add to the pi system from the same
face of the molecule. This is an example of a(n) _________ addition.
Ans: syn
Topic: Alkene Hydrogenation
Section: 7.14
Difficulty Level: Easy
107. How will you prepare cis-1,2-dimethylcyclohexane from 1,2-dimethylcyclohexene?
Ans: Catalytic hydrogenation with H2, Ni (or Pt/Pd)
H2, Ni
Topic: General Information
Section: 7.15
Difficulty Level: Easy
108. Syn hydrogenation of an alkyne will produce a _________ alkene.
Ans: Cis / Z
Topic: General Information
Section: 7.15
Difficulty Level: Medium

289

109. Conversion of alkynes to E-alkenes (trans-alkenes) can be accomplished via a


__________________ reaction.
Ans: dissolving metal reduction

Topic: Alkyne Reduction


Section: 7.15
Difficulty Level: Medium
110. How will you prepare trans-2-heptene from 2-heptyne?
Ans: Dissolving metal reduction with metallic Na in NH3(l).
Na, NH3 (l)
Topic: Nomenclature, Stereochemistry
Section: 4.3, 4.5, 5.7, 7.2
Difficulty Level: Hard
111. Draw the structures of all stereoisomers of 2-chloro-4-methyl-3-hexene, clearly showing
all stereochemical details, using appropriate 3-D representations (dash-wedge, etc.) as
relevant.
2-chloro-4-methyl-3-hexene
Ans:
Cl

(2R, 3E)

Cl

Cl

(2S, 3E)

Topic: Alkene Nomenclature, Relative Stability


Section: 4.5, 7.3
Difficulty Level: Hard

290

(2R, 3Z)

Cl

(2S, 3Z)

112. The ambiguous name dimethylcyclopentene does not clearly distinguish between
several structures.
a) Draw the structures of all constitutional isomers corresponding to this name.
b) Indicate which of these is likely to be the most stable, i.e, have the smallest heat of
combustion, justifying your rationale briefly.
c) Which of these structures represents an achiral molecule?
Ans: a)
dimethylcyclopentene
b)
I
II
III
IV
V
VI
Structure I is likely to be the most stable, because it is a tetra-substituted
alkene: II, IV and V are tri-substituted; III and VI are di-substituted.
c) Structure I is achiral
Topic: Carbocation Rearrangement, Alkene Synthesis, Dehydration Mechanism
Section: 7.7
Difficulty Level: Medium

291

113. Provide a mechanistic explanation for the formation of the observed products in the
following reaction.
H3O+
OH
heat

292

Ans:

1)

2)
293

Topic: Nomenclature, Multistep Synthesis


Section: 4.16, 7.7
Difficulty Level: Hard
114. Propose a two-step synthetic strategy for the synthesis of 2-methylhexane from 5methyl-2-hexanol.
Ans: OH
H3O+
H2
+
Ni
heat
Step 1:
Acid-catalyzed dehydration of 5-methyl-2-hexanol to yield an isomeric mixture of
5-methyl-1-hexene and 5-methyl-2-hexene
Step 2:
Catalytic hydrogenation of the double bond with H2, Ni to yield the desired 2methylhexane
Topic: Carbocation Stability, Rearrangement
Section: 7.8
Difficulty Level: Medium

294

115. What new, more stable, carbocation(s) may be formed when the following
carbocation undergoes spontaneous rearrangement?
Ans:

via a Methyl (methid


Topic: Alkyne Synthesis, Acid-Base reactions
Section: 7.10
Difficulty Level: Medium

295

116. Complete the following reaction sequence, providing a brief rationale for your answer.
O

Ans:

i) PCl5
ii) 3 NaNH2,

mineral oil, heat


iii) H3O+

PCl5

Reaction with PCl5 would afford a geminal dihalide I, which would undergo E2
elimination when heated, losing 2 moles of HCl to afford the alkyne III.
However, since III is a terminal alkyne, it has a hydrogen atom that is labile in
presence of NaNH2; hence, an extra mole equivalent of the base is required to
ensure complete reaction and convert all of the initially formed III into the sodium
alkynide intermediate, II; this, upon acidification, affords the final alkyne product
III.

296

Topic: Nomenclature, Index of Hydrogen Deficiency, IR Spectroscopy, Catalytic Hydrogenation


Section: 2.16, 7.13
Difficulty Level: Medium

297

117. The IR spectrum of an unknown substance Q, C9H16, is found to have distinct peaks at
3310 cm-1 and 2140 cm-1. Treatment of Q with excess H2 in presence of Raney Ni
affords nearly quantitative yields of 2,3-dimethylheptane. Propose a reasonable
structure for Q, based on the above information, briefly explaining your rationale. Also
give its IUPAC name.

298

Ans:

IR: 2140, 3310 cm

Substance Q: 5
dimethyl-1-heptyne
299

Topic: Nomenclature, Multistep Synthesis


Section: 7.11, 7.12, 7.15
Difficulty Level: Medium

300

118. Propose a reasonable synthetic strategy for the synthesis of trans-6-methyl-3-heptene


from 4-methyl-1-pentyne.

301

Ans:

NaNH
NH3 (

302

Topic: Alkyne Synthesis, Alkyne Hydrogenation


Section: 7.11, 7.12, 7.15A
Difficulty Level: Medium
119. Complete the following reaction, giving structural details of all intermediates as well as
the final product.
?
:

Ans:

1) NaNH2, NH3 (l)


NaNH2)2 CH3CH2CH2Br
NH3 (l)
3) H2, Lindlar catalyst

Na

CH3CH2CH2Br
H2
Lindlar catalyst

303