CH 7
CH 7
CH 7
Topic: Nomenclature
Section: 4.3, 4.5, 7.2
Difficulty Level: Easy
A) 2-Bromo-4-methylenehexane
B) 2-(2-Bromopropyl)-1-butene
C) 4-Bromo-2-ethyl-1-pentene
D) 2-Bromo-4-ethyl-1-pentene
E) 2-Bromo-4-ethyl-4-pentene
Ans: C
A) (cis)-3-methoxyhex-3-ene
B) (Z)-4-methoxyhex-4-ene
C) (Z)-3-methoxyhex-3-ene
D) (E)-3-methoxyhex-3-ene
E) 3-methoxyhex-3-ene
Ans: C
130
Topic: Nomenclature; Stereochemistry
Section: 4.3, 4.5, 7.2
Difficulty Level: Medium
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
D) (Z)-4-phenyl-4-methylbut-3-en-1-ol
E) (E)-4-benzylpent-3-en-1-ol
Ans: B
B)
Br
C)
Br
D) Br
131
Topic: Nomenclature; Stereochemistry
Section: 4.3, 4.5, 7.2
Difficulty Level: Medium
B) Br
C)
Br
D) Br
C) Cl
Cl
D) Cl
Cl
E) None of the above
Ans: B
132
Topic: Nomenclature
Section: 4.5, 7.2
Difficulty Level: Easy
A) 3,3,5-trimethyl-2-hexene
B) 3-isobutyl-3-isopropyl-2-propene
C) 3-isobutyl-4-methyl-2-pentene
D) 3-(1-methylethyl)-5-methyl-2-hexene
E) None of the above
Ans: E
Topic: Nomenclature
Section: 4.5, 7.2
Difficulty Level: Easy
A) 4,5-Dimethyl-3-propyl-2-hexene
B) 4,5-Dimethyl-3-propyl-1-hexene
C) 3-(2,3-Dimethylpropyl)-1-hexene
D) 2,3-Dimethyl-4-isopropyl-5-hexene
E) 2,3-Dimethyl-4-propyl-5-hexene
Ans: B
133
Topic: Nomenclature
Section: 4.5, 7.2
Difficulty Level: Easy
B)
C)
D)
E)
Ans: B
Topic: Nomenclature
Section: 4.5, 7.2
Difficulty Level: Medium
10. The correct IUPAC name for the following compound is:
Cl
Br
A) (E)-2-Bromo-3-chloro-5-methyl-2-hexene
B) (E)-2-Bromo-3-chloro-5-methyl-3-hexene
C) (Z)-2-Bromo-3-chloro-5-methyl-3-hexene
D) (Z)-2-Bromo-3-chloro-5-methyl-2-hexene
E) (E)-2-Methyl-5-bromo-4-chloro-4-hexene
Ans: A
134
Topic: Nomenclature; Stereochemistry
Section: 4.3, 4.5, 5.7, 7.2
Difficulty Level: Medium
A) (S,Z)-3-bromo-4-methylhex-2-ene
B) (S)-3-bromo-4-methylhex-2-ene
C) (S,Z)-4-bromo-3-methylhex-4-ene
D) (S,E)-3-bromo-4-methylhex-2-ene
E) (R,E)-3-bromo-4-methylhex-2-ene
Ans: A
Br
A) (S,E)-2,4-dibromo-3-methylpent-2-ene
B) (R,Z)-2,4-dibromo-3-methylpent-2-ene
C) (R,E)-2,4-dibromo-3-methylpent-3-ene
D) (S,E)-2,4-dibromo-3-methylpent-3-ene
E) (R,E)-2,4-dibromo-3-methylpent-2-ene
Ans: E
135
Topic: Nomenclature; Stereochemistry
Section: 4.3, 4.5, 5.7, 7.2
Difficulty Level: Hard
OH
A) (R,Z)-5-phenyloct-5-en-3-ol
B) (R,Z)-5-benzyloct-5-en-3-ol
C) (R,E)-5-phenyloct-5-en-3-ol
D) (R,E)-5-benzyloct-5-en-3-ol
E) (R,E)-5-benzyloct-3-en-6-ol
Ans: B
B)
C)
D)
136
Topic: Nomenclature; Stereochemistry
Section: 4.3, 4.5, 4.6, 5.7, 7.2
Difficulty Level: Medium
A) (S,E)-3-chlorohex-4-en-1-yne
B) (R,E)-3-chlorohex-2-en-5-yne
C) (S,E)-3-chlorohex-2-en-5-yne
D) (R,E)-3-chlorohex-4-en-1-yne
E) (R,E)-3-chloropent-4-en-1-yne
Ans: D
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: A
137
Topic: Alkene Stability, Heats of Hydrogenation and Combustion
Section: 7.3
Difficulty Level: Easy
17. Heats of hydrogenation data would be useful in comparing the relative stabilities of
which of the following substances?
I II III IV V
A) I, II, III
B) III, IV
C) I, II, V
D) 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
138
Topic: Alkene Stability, Heats of Hydrogenation and Combustion
Section: 7.3
Difficulty Level: Easy
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: A
139
Topic: Alkene Synthesis, Reaction Mechanisms
Section: 7.6
Difficulty Level: Easy
21. Which product (or products) would be formed in appreciable amount(s) when trans-1-
bromo-2-methylcyclohexane undergoes dehydrohalogenation upon treatment with
sodium ethoxide in ethanol?
I II III IV
A) I
B) II
C) III
D) IV
E) More than one of these
Ans: B
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
140
Topic: Alkene Synthesis
Section: 7.6
Difficulty Level: Easy
OTs
heat
A) CH3CH2(CH3)C=CHCH3
B) CH3CH2(CH3)CHCH=CH2
C) CH3CH2(CH3)CHCH(OCH2CH3)CH3
D) None of the above
E) No reaction
Ans: A
Cl
A)
Ot-Bu
B)
C)
D)
E)
Ans: E
141
Topic: Alkene Synthesis
Section: 7.6
Difficulty Level: Easy
t-BuOH, t-BuOK
I
A)
B)
C)
D)
142
Topic: Alkene Synthesis
Section: 7.6
Difficulty Level: Easy
A)
B)
C)
D)
143
Topic: Alkene Synthesis
Section: 7.6
Difficulty Level: Easy
heat
A)
B)
C)
D)
E)
Ans: A
144
Topic: Alkene Synthesis
Section: 7.6
Difficulty Level: Easy
A)
B)
C)
D)
E)
Ans: E
145
Topic: Alkene Synthesis
Section: 7.6
Difficulty Level: Medium
A)
B)
C)
D)
146
Topic: Alkene Synthesis, Nomenclature, Reaction Mechanisms
Section: 7.6
Difficulty Level: Medium
Br
heat
A)
OEt
B)
C)
D)
E)
Ans: C
147
Topic: Alkene Synthesis
Section: 7.6
Difficulty Level: Hard
Cl
heat
A)
OEt
B)
C)
D)
E)
Ans: B
148
Topic: Alkene Synthesis
Section: 6.5, 7.6
Difficulty Level: Medium
2. t-BuOH, t-BuOK
OTs
A)
B)
C)
D)
E)
Ans: C
149
Topic: Alkene Synthesis
Section: 6.5, 7.6
Difficulty Level: Hard
2. t-BuOH, t-BuOK
Cl
A)
B)
C)
D)
E)
Ans: D
150
Topic: Alkene Synthesis
Section: 6.5, 7.6
Difficulty Level: Hard
A)
B)
C)
D)
E)
Ans: C
151
Topic: Alkene Synthesis
Section: 6.5, 7.6
Difficulty Level: Hard
A)
B)
C)
D)
E)
Ans: B
152
Topic: Alkene Synthesis, Reaction Mechanisms
Section: 6.5, 6.16, 7.6
Difficulty Level: Medium
37. Which compound listed below would you expect to be the major product when 2-
bromo-2-methylbutane is refluxed with KOH/ethanol?
A) OH
B)
O
C)
D)
E)
Ans: D
153
Topic: Alkene Synthesis
Section: 7.6C
Difficulty Level: Easy
A) (CH3)2C=C(CH3)2
B) (CH3)3CCH=CH2
C) (CH3)2C=CHCH3
D) (CH3)2C=CHCH2CH3
E) None of these
Ans: B
154
Topic: Alkene Synthesis, Reaction Mechanisms
Section: 7.6C
Difficulty Level: Easy
A) O
B)
C)
D) OH
E)
Ans: E
155
Topic: Carbocation Stability, Rearrangement
Section: 7.7
Difficulty Level: Easy
A)
B)
and
C)
and
D)
E)
O
Ans: B
156
Topic: Alkene Synthesis; Alcohol Dehydration
Section: 7.7
Difficulty Level: Easy
44. Which one of the following alcohols would dehydrate most rapidly when treated with
sulfuric acid?
OH OH OH
I II III
OH
OH
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B
157
Topic: Alkene Synthesis; Alcohol Dehydration
Section: 7.7
Difficulty Level: Easy
+ H3O+ + H2O
OH OH2
B) Step 2:
+ H2O
OH2
C) Step 3:
D) Step 4a:
+ H2O + H3O+
E) Step 4b:
+ H 2O + H3O+
Ans: B
158
Topic: Alkene Synthesis; Alcohol Dehydration
Section: 7.7
Difficulty Level: Easy
OH
B) CH3
CH3CH2CHCHCH3
OH
C) CH3
CH3CH2CHCH2CH2OH
D) CH3
HOCH2CHCH2CH2CH3
E) CH2OH
CH3CH2CHCH2CH3
Ans: A
OH OH OH
I II III
OH
OH
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B
159
Topic: Carbocation Stability
Section: 7.7
Difficulty Level: Medium
48. Which alcohol would initially produce the most stable carbocation when treated with
concentrated H2SO4?
A) OH
B)
OH
C)
OH
D)
HO
E) HO
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
160
Topic: Carbocation Stability, Rearrangement
Section: 6.11B, 7.7B
Difficulty Level: Easy
50. Which of the following carbocations would NOT be likely to undergo rearrangement?
A) CH3CHCHCH3
CH3
B) CH3
CH3CHCCH3
CH3
C) CH3
CH3CCH2CH3
D) CH3
CH3CHCH2
E) CH3
CH3CCHCH2CH3
CH3
Ans: C
I II III
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B
161
Topic: Carbocation Stability, Rearrangement
Section: 5.12, 6.10, 6.17, 7.8
Difficulty Level: Medium
52. What is the major product of the reaction between methanol and (2R,3S)-2-bromo-3-
methylpentane at room temperature?
A)
B) OCH3
C)
D)
H3CO
E) Both A) and C)
Ans: D
53. Rearrangements are likely to occur in which of the following reaction types?
A) SN1 reactions
B) SN2 reactions
C) E1 reactions
D) E2 reactions
E) Both SN1 and E1 reactions
Ans: E
162
Topic: Carbocation Stability, Rearrangement
Section: 6.10, 6.17, 7.8
Difficulty Level: Easy
54. What is the major product of the reaction of the following reaction?
I
ethanol, 20 oC
A)
CH3CH2O
B) OCH2CH3
C)
D)
163
Topic: Alkene Synthesis
Section: 6.10, 6.17, 7.8
Difficulty Level: Easy
EtOH, heat
Br
A)
B)
C)
D)
164
Topic: Alkene Synthesis
Section: 6.10, 6.17, 7.8
Difficulty Level: Medium
EtOH, heat
I
A)
B)
C)
D)
165
Topic: Alkene Synthesis
Section: 6.10, 6.17, 7.8
Difficulty Level: Medium
A)
B)
C)
D)
E)
Ans: D
166
Topic: Carbocation Stability, Rearrangement
Section: 6.10, 6.17, 7.8
Difficulty Level: Hard
58. What is the major product of the reaction of the following reaction?
Cl
EtOH, heat
A)
B)
C) OEt
D)
E)
Ans: D
167
Topic: Carbocation Stability, Rearrangement
Section: 6.10, 6.17, 7.8
Difficulty Level: Hard
59. What is the major product of the reaction of the following reaction?
EtOH, heat
OTs
A)
B)
C)
OEt
D)
168
Topic: Carbocation Stability, Rearrangement
Section: 6.10, 6.17, 7.8
Difficulty Level: Hard
60. What is the major product of the reaction of the following reaction?
CH3OH, heat
Cl
A)
H3CO
B)
C)
D)
E)
Ans: E
169
Topic: Carbocation Stability, Rearrangement
Section: 4.16, 6.10, 6.17, 7.3, 7.8
Difficulty Level: Medium
61. What is the major product of the reaction of the following reaction sequence?
Br
1. H2, Ni
2. EtOH, heat
A)
B)
C)
D) OEt
E) A mixture of A) and B)
Ans: C
170
Topic: Alkene Synthesis, Reaction Mechanisms, Carbocation Rearrangements
Section: 7.7, 7.8
Difficulty Level: Medium
62. Which alkene would you expect to be the major product of the following dehydration?
H2SO4
?
heat
OH
I II III
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: C
171
Topic: Alkene Synthesis, Reaction Mechanisms, Carbocation Rearrangements
Section: 7.7, 7.8
Difficulty Level: Hard
B)
C)
D) O
E)
Ans: A
172
Topic: Alkene Synthesis, Nomenclature
Section: 7.6C, 7.7, 7.10
Difficulty Level: Medium
173
Topic: Alkyne Synthesis
Section: 3.6, 7.11, 7.12
Difficulty Level: Hard
66. Which reaction conditions would not yield 2-butyne from 1-propyne?
A) a. EtONa, EtOH
b. CH3I
B) a. CH3Li, THF
b. CH3I
C) a. NaNH2, NH3 (liq)
b. CH3I
D) a. NaCH2CH3, THF
b. CH3I
E) More than one of these
Ans: A
(1 mol)
B) NaNH2 Br
(1 mol)
C) Br
CH3OH
Br
D) HA
heat
OH
E) Br
NaOC2H5
C2H5OH
Ans: B
174
Topic: Alkyne Synthesis
Section: 7.10, 7.11, 7.12
Difficulty Level: Medium
175
Topic: Alkyne Synthesis
Section: 7.11, 7.12
Difficulty Level: Medium
70. Which reaction would not result in alkylation of the acetylide anion?
A) Br
Li
B) Cl
Li
C)
Br
Li
D)
OTs
Li
E) None of the above
Ans: C
71. Which reaction would not primarily proceed via an SN2 mechanism?
A) Br
Li
B) Cl
Li
C)
Br
Li
D)
OTs
Li
E) All of them proceed via SN2
Ans: C
176
Topic: Alkene/Alkyne Reactions, Reaction Mechanisms
Section: 3.16, 7.13
Difficulty Level: Easy
72. Which would be the major product of the following reaction sequence?
1a. NaNH2, NH3 (liq.)
1b. T3O+
2. H2, Pd/C
A)
CH2CH3
B)
CH=CHT
C)
CH=CH2
D)
CH2CH2T
E) None of the above
Ans: D
177
Topic: Index of Hydrogen Deficiency, Catalytic Hydrogenation
Section: 2.16, 4.16, 4.17, 7.13
Difficulty Level: Easy
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:
I II III
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: C
178
Topic: Index of Hydrogen Deficiency, Catalytic Hydrogenation
Section: 2.16, 4.16, 4.17, 7.13
Difficulty Level: Medium
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 2-
methylpentane?
A)
B)
C)
D)
E)
Ans: D
77. Upon catalytic hydrogenation, a compound C6H6 absorbs four moles of hydrogen.
Select a structure for C6H6.
I II III IV V
A) I, II
B) III
C) II, III
D) IV, V
E) I, IV, V
Ans: D
179
Topic: Index of Hydrogen Deficiency, Catalytic Hydrogenation
Section: 4.16, 4.17, 7.13
Difficulty Level: Easy
78. H2, Pt
X (C8H14) Y (C8H16)
Given: 25oC
One can conclude that X 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
I II III
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: D
180
Topic: Alkene Synthesis
Section: 7.10A, 7.13
Difficulty Level: Medium
80. What is the major product for the following reaction sequence?
1a. NaNH2 (excess)
mineral oil, heat
Cl 1b. NH4Cl
Cl
2. H2 (excess), Pd/C
A)
B) C
C)
D)
81. Which would be the major product of the following reaction sequence?
1a. NaNH2 (excess)
Cl mineral oil, heat
Cl
1b. T3O+
H
2. H2, Pd/C
A) (CH3CH2)2C=C=CHT
B) (CH3CH2)2C=C=CH2
C) (CH3CH2)2CHCCT
D) (CH3CH2)2CHCH=CHT
E) None of the above
Ans: E
181
Topic: Alkene Synthesis
Section: 7.11, 7.12, 7.13
Difficulty Level: Medium
82. What is the major product for the following reaction sequence?
1a. NaNH2, NH3 (liq.)
H 1b. CH3CH2CH2Br
H 2. H2 (excess), Pd/C
A)
B)
C)
D) N
H
E) None of the above
Ans: B
83. What is the major product for the following reaction sequence?
1a. NaNH2, NH3 (liq.)
1b. CH3CH2CH2Br
2. H2 (excess), Pd/C
A)
B) CH3CH2CH2Br
C)
D)
182
Topic: Alkene Reactions, Reaction Mechanisms
Section: 4.16, 7.14A
Difficulty Level: Medium
D2, Ni
?
D D CH3
D CH3 H CH3 DD
H D H
I II III
CH3 D
DH D CH3
D H
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: A
183
Topic: Alkene/Alkyne Reactions, Reaction Mechanisms
Section: 7.6, 7.14A
Difficulty Level: Medium
85. Which would be the major product of the following reaction sequence?
1. EtOH, EtONa
2. D2, Pd/C
Br
A)
B)
C)
D
D
H
D)
D
H
D
E)
D
D
Ans: C
184
Topic: Alkene Synthesis, Nomenclature, Reaction Mechanisms
Section: 7.6, 7.7, 7.15
Difficulty Level: Medium
87. What is the major product for the following reaction sequence?
Br
1. NaNH2 (excess)
mineral oil, heat
2. H2, Pd/CaCO3
Br quinoline
A)
B)
C)
D)
E)
Ans: D
185
Topic: Alkene Synthesis
Section: 7.10A, 7.15
Difficulty Level: Medium
88. What is the major product for the following reaction sequence?
1a. NaNH2 (excess)
mineral oil, heat
Cl 1b. NH4Cl
Cl
2. H2, P-2
A)
B) C
C)
D)
89. What is the major product for the following reaction sequence?
1a. NaNH2, NH3 (liq.)
H 1b. CH3CH2CH2Br
A)
B)
C)
D) N
H
E) None of the above
Ans: C
186
Topic: Alkene Synthesis
Section: 7.11, 7.12, 7.15
Difficulty Level: Medium
90. What is the major product for the following reaction sequence?
1a. NaNH2, NH3 (liq.)
H 1b. CH3CH2CH2Br
H 2. H2, Pd/CaCO3
quinoline
A)
B)
C)
D) N
H
E) None of the above
Ans: C
91. What is the major product for the following reaction sequence?
1a. NaNH2, NH3 (liq.)
1b. CH3CH2CH2Br
A)
B) CH3CH2CH2Br
C)
D)
187
Topic: Alkene Synthesis
Section: 7.11, 7.12, 7.15
Difficulty Level: Medium
92. What is the major product for the following reaction sequence?
1a. n-BuLi, THF
1b. CH3CH2CH2Br
2. H2, P-2
A)
B) CH3CH2CH2Br
C)
D)
93. Which of these is the most satisfactory method for the preparation of cis-2-pentene?
A) CH3CHBrCH2CH2CH3 + (CH3)3COK/(CH3)3COH
B) CH3CCCH2CH3 + H2, Pt
C) CH3CCCH2CH3 + H2, Ni2B (P-2)
D) CH3CCCH2CH3 + Li/liq. NH3
E) CH3CH2CHBrCH2CH3 + CH3CH2ONa/CH3CH2OH
Ans: C
188
Topic: Alkyne Synthesis, Nomenclature, Reaction Mechanisms
Section: 7.6, 7.13, 7.15
Difficulty Level: Easy
189
Topic: Alkyne Synthesis, Catalytic hydrogenation
Section: 7.11, 7.15A
Difficulty Level: Medium
96. The structure of the product, C, of the following sequence of reactions would be:
NaNH2 CH3CH2Br H2
A B C
NH3(l) Ni2B [P-2]
A)
B)
C)
D) Br
E)
Ans: A
190
Topic: Alkene/Alkyne Reactions, Reaction Mechanisms
Section: 7.13, 7.15A
Difficulty Level: Medium
97. Which would be the major product of the following reaction sequence?
1. D2, Pd/CaCO3
quinoline
2. H2, Ni
A) D
D
B) D
D
C)
D
D
D)
191
Topic: Alkene/Alkyne Reactions, Reaction Mechanisms
Section: 6.5, 6.16, 7.11, 7.15A
Difficulty Level: Hard
98. Which would be the major product of the following reaction sequence?
1a. NaNH2, NH3 (liq.)
1b. CH2=CHCH2Br
2. D2, P-2
A)
D
D
B)
D D H D
D
H
D D H
C) D
D
D)
192
Topic: Dissolving Metal Reduction; trans-hydrogenation
Section: 7.15B
Difficulty Level: Easy
99. The structure of the product obtained from 2-butyne and Li/C2H5NH2 is:
A)
B)
C)
HN
D)
NH
E)
Ans: A
193
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
101. When an elimination reaction gives the less substituted alkene as the major product, we
say that the elimination follows ________________'s rule.
Ans: Hofmann
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
194
Topic: General Information
Section: 7.10
Difficulty Level: Medium
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
195
Topic: Alkyne Reduction
Section: 7.15
Difficulty Level: Medium
Cl H H Cl Cl H H Cl
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
I II III IV V VI
196
Topic: Carbocation Rearrangement, Alkene Synthesis, Dehydration Mechanism
Section: 7.7
Difficulty Level: Medium
113. Provide a mechanistic explanation for the formation of the observed products in the
following reaction.
H3O+
OH
heat
Ans: H
: :
:O H
:
1) OH OH2 :O H
:
H H
rearrangement
2) OH2+
[-H2O]
:
H
3a) :O H
:
:O H
H H H
H
Both
H
H H H
3b) :O H
:
:O H
H H
114. Propose a two-step synthetic strategy for the synthesis of 2-methylhexane from 5-
methyl-2-hexanol.
Ans: OH
H3O+ H2
+
heat Ni
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 2-
methylhexane
197
Topic: Carbocation Stability, Rearrangement
Section: 7.8
Difficulty Level: Medium
115. What new, more stable, carbocation(s) may be formed when the following
carbocation undergoes spontaneous rearrangement?
Ans:
116. Complete the following reaction sequence, providing a brief rationale for your answer.
O
i) PCl5
?
ii) 3 NaNH2,
mineral oil, heat
iii) H3O+
Ans: O Cl Na
Cl
PCl5 3 NaNH2, H3O+
mineral oil, heat
I (-2HCl) II III
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.
198
Topic: Nomenclature, Index of Hydrogen Deficiency, IR Spectroscopy, Catalytic Hydrogenation
Section: 2.16, 7.13
Difficulty Level: Medium
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.
Ans: H
excess H2
Ni
Substance Q: 5,6-
dimethyl-1-heptyne
199
Topic: Nomenclature, Multistep Synthesis
Section: 7.11, 7.12, 7.15
Difficulty Level: Medium
Li, NH3(l)
Step 1:
Add NaNH2/NH3(l) to selectively deprotonate the alkyne hydrogen.
Step 2:
Add ethyl iodide to give 6-methyl-3-pentyne by an SN2 process.
Step 3:
Add Na(s)/NH3(l) to give the desired trans-alkene by dissolving metal reduction.
119. Complete the following reaction, giving structural details of all intermediates as well as
the final product.
CH3CH2CH2Br
H2
Lindlar catalyst
200