CH 07
CH 07
CH 07
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
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
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
Br
B)
Br
134
C)
Br
D)
Br
135
Br
B)
C)
D)
Br
Br
Br
136
137
Cl
Cl
B)
Cl
138
C)
Cl
Cl
D)
E) None of the above
Ans: B
Cl
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
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
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
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
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
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
B)
144
C)
145
D)
146
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
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
I
II
III
IV
V
Ans: A
II
III
IV
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
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
tCl
151
A)
Ot-Bu
B)
C)
152
D)
E)
Ans: E
153
154
A)
155
B)
156
C)
157
D)
E)
None of the above
Ans: D
158
E
I
159
A)
160
B)
161
C)
162
D)
163
27.
Cl
164
A)
165
B)
166
C)
167
D)
168
E)
Ans: A
169
Br
170
A)
171
B)
172
C)
173
D)
174
E)
Ans: E
175
E
Br
176
A)
177
B)
178
C)
179
D)
180
E
Br
181
A)
OEt
B)
C)
182
D)
E)
Ans: C
183
E
Cl
184
A)
OEt
B)
C)
185
D)
E)
Ans: B
186
1.
OTs
A)
B)
187
2.
C)
D)
188
E)
Ans: C
189
1.
Cl
A)
B)
190
2.
C)
D)
191
E)
Ans: D
192
1.
Cl
A)
B)
193
2.
C)
D)
194
E)
Ans: C
195
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
(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
A)
B)
C)
D)
E)
OH
Ans: E
199
42.
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
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+
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
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)
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
Br
210
A)
211
B)
212
C)
213
D)
214
215
A)
216
B)
217
C)
218
D)
219
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
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. NaCH2CH3, THF
b. CH3I
E) More than one of these
Ans: A
237
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)
239
70. Which reaction would not result in alkylation of the acetylide anion?
A)
Li
B)
Li
240
C)
Li
D)
Li
241
242
71. Which reaction would not primarily proceed via an SN2 mechanism?
A)
Li
B)
Li
243
C)
Li
D)
Li
244
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
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)
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)
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)
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)
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
95.
A)
B)
C)
D)
E)
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)
282
98. Which would be the major product of the following reaction sequence?
283
A)
D
D
284
B)
285
C)
286
D)
287
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
289
(2R, 3E)
Cl
Cl
(2S, 3E)
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
294
115. What new, more stable, carbocation(s) may be formed when the following
carbocation undergoes spontaneous rearrangement?
Ans:
295
116. Complete the following reaction sequence, providing a brief rationale for your answer.
O
Ans:
i) PCl5
ii) 3 NaNH2,
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
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:
Substance Q: 5
dimethyl-1-heptyne
299
300
301
Ans:
NaNH
NH3 (
302
Ans:
Na
CH3CH2CH2Br
H2
Lindlar catalyst
303