ch09

Chapter 9
Multiple Choice Questions:
Topic: Addition Reaction Mechanisms

Section: 9.1
Difficulty Level: Easy
1. In an addition reaction to an alkene, the π bond plays the role of:

A) nucleophile
B) electrophile
C) leaving group
D) A and B
E) B and C
Ans: A
Topic: Addition Reaction Mechanisms

Section: 9.1
Difficulty Level: Moderate
2. Addition reactions of alkenes are characterized by:

A) formation of a π bond
B) addition of two groups across a double bond
C) breaking of a π bond
D) A and B
E) B and C
Ans: E
Topic: Addition vs. Elimination Thermodynamic Perspective
Section: 9.2
3. The decrease in entropy (the S value is negative) observed for alkene addition
reactions results from:
A) the breaking of a π and  bond.
B) the formation of two  bonds.
C) the reaction being exothermic.
D) two molecules reacting to form a single molecule.
E) the temperature dependence of the S term.
Ans: D

Section: 9.2
4. In a reaction where addition and elimination reactions are in competition, which of

the following statements is most correct?
A) Addition and elimination reactions are favored at low temperatures.
B) Addition and elimination reactions are favored at high temperatures.
C) Only addition reactions are favored at low temperatures.
D) Only elimination reactions are favored at low temperatures.
E) Addition and elimination reactions are disfavored at low temperatures.
Ans: C

Section: 9.2
5. Which statement is true about the temperature dependence of an addition reaction?

A) Addition reactions are thermodynamically favorable at all temperatures.
B) Addition reactions are thermodynamically disfavored at all temperatures.
C) Addition reactions are thermodynamically favorable at low temperatures.
D) Addition reactions are thermodynamically favorable at high temperatures.
E) Addition reactions are thermodynamically impossible.
Ans: C
Section: 9.2
6. For an addition reaction, why does the free energy term, G, become more positive
with increasing temperature?
A) The positive entropy term dominates at high temperature.
B) The negative entropy term dominates at high temperature.
C) The positive enthalpy term dominates at high temperature.
D) The negative enthalpy term dominates at high temperature.
E) The enthalpy and entropy terms cancel at high temperature.
Ans: A

Section: 9.2
Difficulty Level: Hard
7. Addition reactions are favorable at low temperatures because:

A) the positive enthalpy term is larger than the negative entropy term.
B) the negative enthalpy term is larger than the positive entropy term.
C) the positive enthalpy term is smaller than the negative entropy term.
D) the negative enthalpy term is smaller than the positive entropy term.
E) the enthalpy and entropy terms are equal.
Ans: B
Topic: Hydrohalogenation
Section: 9.3
8. Which of the molecules below would be the expected product for

hydrohalogenation of the following alkene:
A)
B)
C)
D)
E)
Ans: E
Section: 9.3
9. In the addition reaction of HI to 2-methyl-2-butene, the Markovnikov addition

mechanism involves:
A) attack of 2-methyl-2-butene initiated by an iodide ion.
B) attack of 2-methyl-2-butene initiated by an iodine atom.
C) isomerization of 2-iodo-2-methylbutene.
D) formation of a carbocation at carbon two (C-2).
E) formation of carbocation at carbon three (C-3).
Ans: D
Section: 9.3
10. The expected Markovnikov addition product of HI to 2-methyl-2-butene is:

A) 2-iodopentane
B) 2-iodo-2-methylbutane
C) 1-iodo-2-methylbutane
D) 2-iodo-1-methylbutane
E) 3-iodo-2-methylbutane
Ans: B
Section: 9.3
11. The regioselectivity and stereospecificity in hydrohalogenation of an alkene is best

described as:
A) Markovnikov orientation with syn-addition
B) Markovnikov orientation with anti-addition
C) anti-Markovnikov orientation with syn-addition
D) anti-Markovnikov orientation with anti-addition
E) Markonikov orientation with both syn- and anti-addition
Ans: E
Section: 9.3
12. Which of the structures shown depicts the most stable carbocation intermediate
formed in a hydrohalogenation reaction?
A) I
B) II
C) III
D) IV
E) V
Ans: B
Section: 9.3
13. What compound is the expected product upon Markovnikov hydrohalogenation

with HBr of the alkene shown below?
A)
B)
C)
D)
E)
Ans: B
Section: 9.3
14. The expected major product of the following reaction is:
A)
B)
C)
D)
E)
Ans: C
Section: 9.3
A)
B)
C)
D)
E)
Ans: A
Section: 9.3
16. What is the expected major product for the following reaction?
A) I
B) II
C) III
D) IV
E) V
Ans: D
Topic: Anti-Markovnikov Hydrohalogenation
Section: 9.3
17. Which of the molecules below arises from anti-Markovnikov hydrohalogenation

with HBr of the alkene shown?
A)
B)
C)
D)
E)
Ans: C
Topic: Stereochemistry of Hydrohalogenation

Section: 9.3
18. Which of the alkenes shown below would produce a chirality center upon
hydrohalogenation?
A)
B)
C)
D)
E)
Ans: B
Section: 9.3
19. What is the major product for the following reaction?
A)
B)
C)
D)
E)
Ans: A

Section: 9.3
20. Which of the alkenes below would be expected to produce a chirality center upon
hydrohalogenation in the presence of peroxide?
A)
B)
C)
D)
E)
Ans: B
Section: 9.3
21. Which of the given reaction schemes would produce the molecule shown below?
A)
B)
C)
D) Both A and B
E) Both B and C
Ans: E

Section: 9.3
22. Which of the molecules below are enantiomers, formed as products upon reaction
of HBr with 4-methylpent-1-ene?
A) I and II
B) II and III
C) III and IV
D) I and III
E) II and IV
Ans: E
Topic: Hydrohalogenation and Carbocation Rearrangements
Section: 9.3
23. Which of the following carbocations is likely to undergo rearrangement through a

methyl shift?
A) I
B) II
C) III
D) I and II
E) II and III
Ans: D

Section: 9.3
24. Which of the following carbocations is likely to undergo rearrangement through a

hydride shift?
A) I
B) II
C) III
D) I and II
E) II and III
Ans: D
Section: 9.3
25. The expected major product(s) of HCl addition to the alkene shown would be:
A) I and II
B) II and III
C) I and IV
D) V
E) All of the above are equally likely to form
Ans: A

Section: 9.3
26. The expected major product(s) of HBr addition to the alkene shown would be:
A)
B)
C)
D)
E)
Ans: A
Topic: Stereochemistry of Hydrohalogenation and Carbocation Rearrangements
Section: 9.3
27. The reaction shown below would be expected to produce as major products which
of the following compounds?
A)
B)
C)
D)
E)
Ans: D

Section: 9.3
28. What is the IUPAC name of the expected major product formed upon reaction of
HCl with 3-methyl-1-butene?
A) 1-Chloro-2-methylbutane
B) 1-Chloro-3-methylbutane
C) 2-Chloro-2-methylbutane
D) 2-Chloro-3-methylbutane
E) 1-Chloropentane
Ans: C
Section: 9.3
29. Select the expected major product(s) of the following reaction:
A)
B)
C)
D) A and B
E) A and C
Ans: C

Section: 9.3
30. Identify the expected product(s) for the reaction shown below?
A)
B)
C)
D)
E)
Ans: C
Topic: Acid Catalyzed Hydration
Section: 9.4
31. The regioselectivity and stereospecificity in the acid-catalyzed hydration of an

alkene is best described as:
Ans: E

Section: 9.4
A) I
B) II
C) III
D) IV
E) V
Ans: D
Section: 9.4
A) I
B) II
C) III
D) IV
E) V
Ans: C

Section: 9.4
A)
B)
C)
D)
E)
Ans: D
Section: 9.4
35. Treatment of 1-methylcyclohexene with H3O+ would be expected to yield as the

major product which of the molecules below?
A) I and III
B) II
C) III and V
D) IV
E) I, III and V
Ans: D

Section: 9.4
36. Treatment of (S)-6-chloro-1-methyl-1-cyclohexene with H3O+ is expected to

produce which of the following?
A) I and III
B) II
C) III and V
D) IV
E) I, III and V
Ans: B
Section: 9.4
A)
B)
C)
D)
E)
Ans: A
Topic: Oxymercuration-Demercuration
Section: 9.5
38. The regioselectivity and stereospecificity in the oxymercuration-demercuration of

an alkene is best described as:
Ans: B
Section: 9.5
A)
B)
C)
D)
E)
Ans: B
Section: 9.5
40. What synthetic goal is achieved by subjecting an alkene to an oxymercuration-

demercuration reaction sequence?
A) Markovnikov addition of H2O, promoting skeletal rearrangement
B) Markovnikov addition of H2O, preventing skeletal rearrangement
C) anti-Markovnikov addition of H2O, promoting skeletal rearrangement
D) anti-Markovnikov addition of H2O, preventing skeletal rearrangement
E) anti-Markovnikov addition of H2O, syn-hydroxylation
Ans: B
Section: 9.5
A)
B)
C)
D)
E)
Ans: C
Section: 9.5
A)
B)
C)
D)
E)
Ans: D
Section: 9.5
A)
B)
C)
D)
E)
Ans: B
Section: 9.5
44. When an alkene is subjected to treatment with Hg(OAc) 2 in alcohol, followed by

reaction with NaBH4, what functional group is formed?
A) ether
B) epoxide
C) alkane
D) syn diol
E) alkyne
Ans: A
Topic: Hydroboration-Oxidation
Section: 9.6
45. The regioselectivity and stereospecificity in the hydroboration-oxidation of an

alkene is best described as:
C) Anti-Markovnikov orientation with syn-addition
D) Anti-Markovnikov orientation with anti-addition
E) Markovnikov orientation with both syn- and anti-addition
Ans: C
Section: 9.6
46. What reagents are needed to accomplish the following transformation?
A) H2O/H+
B) H2O/Peroxide
C) OH–
D) BH3
E) 1. BH3, 2. HO–, H2O2, H2O
Ans: E
Section: 9.6
47. What is the expected major product for the following reaction sequence?
A)
B)
C)
D)
E)
Ans: E
Section: 9.6
A) I
B) II
C) III
D) I and II
E) I and III
Ans: E
Section: 9.6
A)
B)
C)
D)
E)
Ans: E
Section: 9.6
A) I
B) II
C) III
D) IV
E) V
Ans: D
Section: 9.6
A)
B)
C)
D)
E)
Ans: B
Topic: Catalytic Hydrogenation
Section: 9.7
52. What is the expected major product for the hydrogenation of an alkene?
A) dihaloalkane
B) alkane
C) haloalkane
D) alcohol
E) ether
Ans: B

Section: 9.7
53. Provide the major organic product(s) for the reaction shown below.
A)
B)
C)
D)
E)
Ans: B

Section: 9.7
54. What product is formed when 5-chloro-1-methylcyclohexene is reduced with a Pt

catalyst and H2?
A) 1-chloro-5-methylcyclohexane
B) 1-chloro-3-methylcyclohexane
C) 5-chloro-1-methylcyclohexane
D) 3-chloro-1-methylcyclohexane
E) None of the above
Ans: B
Section: 9.7
55. What product is formed when trans-1,2-dimethylcyclohexane is reacted with Pd/C

and H2?
A) No reaction
B) cis-1,2-dimethylcyclohexane
C) trans-3,4-dimethylhexane
D) trans-1,2-dimethylhexane
Ans: A

Section: 9.7
56. Which of the following reagents accomplishes the transformation shown below?
A) H2/HCl
B) H2/H2SO4
C) H2/Ni
D) H2O/Ni
E) H2O/H2SO4
Ans: C

Section: 9.7
57. Which of the reagents below are expected to convert cyclopentene into
cyclopentane?
A) H2 and Ni
B) H2O
C) Heat
D) Zn, H3O+
E) Light
Ans: A
Section: 9.7
58. Which alkene would yield 3-methylpentane upon subjection to catalytic

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

Section: 9.7
59. How many moles of hydrogen (H2) are consumed in the catalytic reduction of 1
mole of 1,3-dibromocyclohexa-1,4-diene?
A) 1
2
B) 2
C) 3
D) 4
Ans: B

Section: 9.7
60. How many moles of hydrogen (H2) are required to completely reduce 1 mole of cis-
2,3,3-trimethylhepta-1,5-diene?
A) 0
2
B) 1
C) 2
D) 3
E) 4
Ans: C
Section: 9.7
61. Which of the catalysts listed are used in the homogenous catalytic hydrogenation of
alkenes?
I) Ni II) Pt III) Wilkinson
A) I
B) II
C) III
D) I and II
E) II and III
Ans: C

Section: 9.7
62. In conducting a catalytic hydrogenation of an alkene, which catalyst listed is most

likely soluble in the reaction medium?
A) Ni
B) Pt
C) Pd
D) Wilkinson
E) All of the above are soluble
Ans: D

Section: 9.7
63. Wilkinson’s catalyst accomplishes which of the listed molecular transformations?

A) syn addition of H2 to an alkene
B) anti addition of H2 to an alkene
C) syn dihydroxylation of an alkene
D) anti dihydroxylation of an alkene
E) oxidative cleavage of an alkene
Ans: A
Section: 9.7
64. For the catalytic hydrogenation of alkenes, select from below those most likely to
function as a homogenous catalyst?
A) Wilkinson
B) Ni
C) Pd
D) Pt
E) Au
Ans: A

Section: 9.7
65. Which of the following will yield 2-methylpentane upon catalytic hydrogenation?
A) 2-methyl-1-pentene 2
B) 2-methyl-2-pentene
C) 4-methyl-2-pentene
D) 4-methyl-1-pentene
E) All of the above
Ans: E

Section: 9.7
66. For the complete reduction of 1 mole of (3E,5E)-hepta-1,3,5-triene with H2 using a

Pd catalyst, how many moles of H2 are consumed?
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: C
Topic: Catalytic Hydrogenation and Stereospecificity
Section: 9.7
67. What products are produced from the reaction below?
A) I, II, III
B) II, III, IV
C) I and IV
D) II and III
E) I, II, III, and IV
Ans: A
Topic: Catalytic Hydrogenation and Stereospecificity

Section: 9.7
68. Identify the major organic product generated from the reaction shown.
A) I
B) II
C) III
D) IV
E) V
Ans: B
Topic: Halogenation
Section: 9.8
69. Which reaction intermediate is formed when 4-methylcyclohexene reacts with Br2
dissolved in CCl4?
A) I
B) II
C) III
D) IV
E) V
Ans: B
Topic: Halogenation
Section: 9.8
70. What is the expected major product upon reaction of 1-pentene with Cl2?
A) 1-chloropentane
B) 2-chloropentane
C) 1,1-dichloropentane
D) 2,2-dichloropentane
E) 1,2-dichloropentane
Ans: E
Topic: Halogenation and Stereospecificity

Section: 9.8
71. Treating 2-methyl-2-pentene with Br2 is expected to produce which of the

following as the major product?
A) 2,3-dibromo-2-methylpentane
B) 2,2-dibromo-2-methylpentane
C) 3,3-dibromo-2-methylpentane
D) 2-bromo-2-methylpentane
E) 3-dibromo-2-methylpentane
Ans: A
Topic: Halohydrin Formation
Section: 9.8
72. The expected intermediate formed during a halohydrin reaction is:

A) a halonium ion.
B) the most stable carbocation with OH on the adjacent carbon.
C) the most stable carbocation with X on the adjacent carbon.
D) a cyclic oxonium ion.
E) the most stable carbanion.
Ans: A

Section: 9.8
73. What major product is expected from the following reaction?
A) I
B) II
C) III
D) IV
E) V
Ans: D
Section: 9.8
A) I
B) II
C) III
D) IV
E) V
Ans: D

Section: 9.8
75. Which of the statements is most correct regarding the products expected from the
halogenation reaction shown below?
A) Equal amounts of I and II are produced.

B) Equal amounts of III and IV are produced.
C) Equal amounts of I and IV are produced.
D) Equal amounts of II and III are produced.
E) Equal amounts of I and III are produced.
Ans: B
Section: 9.8
76. For the halogenation reaction shown below, which of the following statements is
correct regarding the expected products?
A) Equal amounts of I and II produced

B) Equal amounts of III and IV produced
C) Equal amounts of I and IV produced
D) Equal amounts of II and III produced
E) Equal amounts of I and III produced
Ans: A
Topic: Halogenation, Regioselectivity, and Stereospecificity

Section: 9.8
77. The reaction of Br2 with 1-methylcyclohexene, in the presence of ethylamine

(EtNH2), is expected to produce which of the following as the major product?
A) I
B) II
C) III
D) IV
E) V
Ans: D
Topic: anti dihydroxylation
Section: 9.9
78. For the reaction sequence below, identify the expected major products.
A)
B)
C)
D)
E)
Ans: B

Section: 9.9
79. For the reaction sequence below, identify the expected major product(s).
A) I
B) II
C) III
D) I and III
E) II and III
Ans: D
Section: 9.9
80. What are the major products for the following reaction sequence?
A) I and II
B) II and III
C) III and IV
D) I and III
E) II and IV
Ans: E

Section: 9.9
81. What is the major product for the following reaction sequence?
A) I
B) II
C) III
D) IV
E) V
Ans: D
Section: 9.9
82. For the following dihydroxylation reaction which of the following statements is
correct regarding the expected products?
A) Equal amounts of I and II produced

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

Section: 9.9
83. An unknown alkene was reacted with MCPBA in dichloromethane, followed by

work-up with H2O/H+. A racemic mixture of the compound shown below was
obtained. What is correct name of the starting alkene?
A) (Z)-3-methylpent-2-ene
B) (E)-3-methylpent-2-ene
C) 2-methylpent-2-ene
D) 2,3-dimethylbut-2-ene
E) none of the above
Ans: A
Topic: syn Dihydroxylation
Section: 9.10
84. Identify the expected major organic product resulting from the following reaction
sequence.
A) I
B) II
C) III
D) IV
E) V
Ans: A

Section: 9.10
85. Treatment of 1,2-dimethylcyclopentene with OsO4, followed by aqueous NaHSO 3,

produces which of the following:
A) I
B) II
C) III
D) IV
E) V
Ans: A
Section: 9.10
86. Identify the expected major organic product generated from the reaction sequence
shown.
A) I
B) II
C) III
D) IV
E) V
Ans: B

Section: 9.10
87. Which of the following alkene addition reactions occur(s) specifically in syn
fashion?
A) dihydroxylation using OsO4, H2O2
B) addition of H2
C) hydroboration
D) addition of HCl
E) A, B, and C
Ans: E
Section: 9.10
A)
B)
C)
D)
Ans: A
Topic: Oxidative Cleavage

Section: 9.11
89. Provide the expected major organic product of the reaction sequence shown.
A) I and II
B) IV and V
C) I only
D) II only
E) III only
Ans: E
Section: 9.11
90. Which of the following reagents effectively cleaves a carbon-carbon double bond?
A) Cl2/hυ
B)
C) H2SO4
D) cold KMnO4
E) O3/DMS
Ans: E

Section: 9.11
91. How many carbonyls are generated upon treatment of the molecule below with
ozone, followed by zinc metal and water?
A) 1
B) 2
C) 3
D) 4
E) 8
Ans: E
Section: 9.11
92. Of the alkenes shown, which would produce the product shown below, upon
treatment with ozone, followed by zinc metal and water?
A) I
B) II
C) III
D) IV
E) V
Ans: B

Section: 9.11
93. What is the expected major product of the reaction sequence shown below?
A) I
B) II
C) III
D) IV
E) V
Ans: A
Section: 9.11
94. What are the expected major products from the reaction sequence shown below?
A) I
B) II
C) III
D) IV
E) V
Ans: A
Topic: Predicting Addition Products
Section: 9.12
95. Which of the following alkene addition reactions occur(s) specifically in an anti
fashion?
A) hydroboration-oxidation
B) addition of Br2
C) addition of H2
D) addition of H2O in dilute acid
E) both A and B
Ans: B

Section: 9.12
96. The Markovnikov product, resulting from an addition reaction to an unsymmetrical

alkene, is formed because:
A) the product is statistically favored.
B) steric hindrance favors its formation.
C) the reaction proceeds via the more/most stable carbocation.
D) the reaction forms the more/most stable product.
E) All of the above are valid reasons
Ans: C

Section: 9.12
A)
B)
C)
D)
E)
Ans: A
Section: 9.12
98. What reagents are most likely to accomplish the transformation shown below?
A) 1. BH3 / 2. HO–, H2O2, H2O

B) H+, H2O
C) 1. Hg(OAc)2, H2O, THF / 2. NaBH4
D) 1. Hg(OAc)2, CH3OH / 2. NaBH4
E) NaOH, H2O
Ans: A

Section: 9.12
99. Which reaction is not stereospecific?
A) I
B) II
C) III
D) IV
E) V
Ans: C
Section: 9.12
100. The expected product(s) resulting from addition of Br2 to (E)-3-hexene would be:
A) a meso dibromide.
B) a mixture of optically active enantiomeric dibromides.
C) a mixture of optically inactive enantiomeric dibromides.
D) (Z)-3,4-dibromo-3-hexene.
E) (E)-3,4-dibromo-3-hexene.
Ans: A

Section: 9.12
101. Which of the following alkenes will yield a meso dihalide when reacted with
Br2/CCl4 at room temperature?
A)
B)
C)
D)
E) Both B and D
Ans: B
Section: 9.12
102. What is the expected major product resulting from the acid-catalyzed hydration of
2,5-dimethyl-2-hexene?
A)
B)
C)
D)
E)
Ans: B

Section: 9.12
103. What is the expected major product resulting from treatment of (E)-3-methyl-3-
hexene with Br2 in the presence of methanol, CH3OH?
A)
B)
C)
D)
E) All of the above are produced in equal amounts
Ans: A
Topic: Synthetic Strategies
Section: 9.13
104. To accomplish a Markovnikov addition of water to an unsymmetrical alkene, with

minimal skeletal rearrangement, the best reagents would be:
A) water and dilute acid
B) water and concentrated acid
C) 1. Hg(OAc)2, H2O 2. NaBH4, NaOH
D) 1. BH3•THF 2. H2O2, NaOH
E) 1. OsO4, pyridine 2. NaHSO3, H2O
Ans: C

Section: 9.13
105. For the reaction sequence shown, what is the expected major elimination product?
A) I
B) II
C) III
D) IV
E) V
Ans: B
Section: 9.13
106. For the reaction sequence shown, what is the expected major elimination product?
A) I
B) II
C) III
D) IV
E) V
Ans: D

Section: 9.13
107. What is the expected major product of the following reaction sequence?
A) I
B) II
C) III
D) IV
E) V
Ans: C
Section: 9.13
A) I
B) II
C) III
D) IV
E) V
Ans: A
Topic: Synthetic Strategies, anti Dihydroxylation

Section: 9.13, 9.9
109. Which is the correct sequence of reaction steps necessary to complete the following
transformation?
A) I then II then III

B) II then I then III
C) II then IV
D) III then I
E) I then IV then II then III
Ans: B
Section: 9.13
A) I
B) II
C) III
D) IV
E) V
Ans: C
Section: 9.13
A)
B)
C)
D)
E)
Ans: A
Section: 9.13
A)
B)
C)
D)
E)
Ans: A
Section: 9.13
A)
B)
C)
D)
E)
Ans: C
Section: 9.13
A)
B)
C)
D)
E)
Ans: A
Section: 9.13
A) I
B) II
C) III
D) IV
E) V
Ans: C

Section: 9.13
116. For the following reaction sequence, which molecule is an expected major product?
A)
B)
C)
D)
E)
Ans: A
Section: 9.13
A)
B)
C)
D)
E)
Ans: E
Section: 9.13
118. For the following reaction sequence identify the expected major organic products
and provide their stereochemical relationship.
A) I and II; enantiomers

B) III and IV; enantiomers
C) I and II; diastereomers
D) II and III; diastereomers
E) III and IV; diastereomers
Ans: D

Section: 9.13
119. For the following reaction sequence identify the total number, frequency and types
of stereoisomeric compounds expected as products.
A) 2 total stereoisomers; 1 set of enantiomers

B) 4 total stereoisomers; 2 sets of enantiomers
C) 4 total stereoisomers; 4 diastereoisomers
D) 8 total stereoisomers; 4 sets of enantiomers
E) 8 total stereoisomers; 8 diastereomers
Ans: E
Short Answer Questions:
Topic: Introduction to Addition Reactions

Section: 9.1
120.  bonds are quite susceptible to reaction with electron-seeking reagents, also
referred to as ____________________.
Ans: electrophiles
Topic: Regioselectivity
Section: 9.3
121. The rule that correctly predicts the regiochemistry of most ionic additions to
alkenes is called ____________________.
Ans: Markovnikov's Rule
Section: 9.3
122. For the following reaction sequence provide the expected major organic product(s).
Include all stereoisomers showing relevant stereochemistry.
Ans:
Section: 9.3
123. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:
Ans:
Section: 9.3
124. The reaction of HCl with 2-ethyl-1-pentene or HCl with 3-methyl-2-hexene results
in the identical major product of 3-chloro-3-methylhexane. Provide a mechanistic
scheme showing the reaction of each alkene with HCl, including the intermediate
and product. Provide a brief explanation how the different alkene reactants were
transformed into the same product.
Ans:
Electrophilic addition of a proton in the reaction between HCl and both alkenes
will result in formation of the most stable intermediate carbocation. Addition of
Cl– to the tertiary carbocation formed in both cases results in the observed
product. The reason for the identical major product is a consequence of
regioselective addition to the double bond forming the same tertiary carbocation
intermediate.

Section: 9.3
125. When the two constitutional isomers, 3,3-dimethyl-1-butene and 2,3-dimethyl-2-

butene, are reacted with HCl the same major product is formed. Provide a
mechanistic explanation for the observation.
Ans:
For the unsymmetrical 3,3-dimethyl-1-butene, the carbocation formed is 2°, but

can readily undergo a methyl shift to form the more stable 3° carbocation, which
is the same as that formed from 2,3-dimethyl-2-butene. The addition of the
chloride ion to the carbocation forms the identical product, 2-chloro-2,3-
dimethylbutane.
Section: 9.3
126. Addition of HI to the alkene of the cyclobutane in the scheme below, results in a
significant yield of the product shown. What other product(s) might also be
obtained? Explain with a mechanism and brief discussion the observation of the
given product as well as others that may arise.
Ans:
Regioselective addition of the proton of HI generates a secondary
carbocation. Rearrangement to a more stable 3o carbocation can occur by
two alternative pathways (1 and 2). Pathway 1 results in relief of ring
strain by expansion to a more stable 5-membered ring. The second
pathway involving a methyl shift is less likely; ring strain is not relieved
and becomes worse with incorporation of an sp2 carbon (bond angle 120°)
into the cyclobutane (bond angle 90°). The third pathway occurs if
addition of iodide to occurs before carbocation rearrangement. The first
pathway is most likely, resulting in the observed product.
Topic: Acid-Catalyzed Hydration
Section: 9.4
Include all stereoisomers showing relevant stereochemistry.
Ans:

Section: 9.4
Include all stereoisomers and clearly show relevant stereochemistry.
Ans:

Section: 9.4
Ans:
Section: 9.4
130. The transformation shown below generates an achiral product from a chiral starting
material. Provide the structure of the expected product and a mechanism
explaining the transformation. Briefly explain why the product formed is achiral.
Ans:
Upon addition of the proton to the alkene a 2° carbocation is formed that

undergoes a hydride shift to form a more stable 3° carbocation. The 3°
carbocation is located in the center of the chain, and being sp2 hybridized
is planar. Addition of water to the central carbon produces a product with
no stereocenter and is thus achiral.
Section: 9.6
131. A reaction that could potentially yield two or more constitutional isomers, but as in
hydroboration-oxidation produces only one isomer, is said to be
_____________________.
Ans: regioselective
Section: 9.6
132. Any proper mechanism of hydroboration-oxidation must explain the observed

_________ addition of the H and OH to the alkene as well as the _____________
regiochemistry.
Ans: syn, anti-Markovnikov

Section: 9.6
Ans:

Section: 9.8
134. Provide the expected major organic product from the reaction shown below.
Provide a brief explanation of any regioselectivity the reaction is expected to
produce.
Ans:
The alcohol will be found at the tertiary carbon, being the more substituted
carbon. Initial formation of the bromonium ion will favor attack of the
water at the more substituted carbon which is more capable of stabilizing
the partial positive charge that develops in the transition state.

Section: 9.8
135. For the following transformation below, provide a detailed step-wise mechanism
showing the electron flow using the curved arrow formalism.
Ans:
Section: 9.8
136. For the following reaction draw out the expected major organic product(s). Include
regiochemical and/or stereochemical details as relevant, and provide a short
justification for the product(s) drawn.
Ans:
The reaction takes place with Markovnikov regioselectivity and anti
stereospecificity, giving a racemic mixture of the halohydrin as the major
product.

Section: 9.8
137. Draw Fischer projection formulas of the major product of the reaction between
(E)-2-methyl-3-hexene and aqueous Br2.
Ans:
The reaction takes place with anti stereospecificity. Since the alkene is
symmetrically substituted, Markovnikov rule is not applicable, and the
reaction is not regioselective. The product mixture would therefore consist
of 2 pairs of enantiomers, which are constitutional isomers of each other.
Section: 9.11
Ans:
and
Topic: Predicting Reaction Products: Halohydrin Formation and Stereospecificity

Section: 9.12
139. Predict the structure(s) of the expected major organic product(s) of the following
reaction. Include regiochemical and/or stereochemical details as needed.
Ans:
stereospecificity. As the product is chiral, the products are diastereomers.
Topic: Predicting Reaction Products: syn Dihydroxylation

Section: 9.12
140. Draw Fischer projection formula(s) of the major product(s) of the reaction between
(Z)-2-methyl-3-hexene and cold, alkaline KMnO4.
Ans:
The reaction takes place with syn stereospecificity, giving a racemic
mixture of the diol product.
Topic: Predicting Reaction Products: syn Dihydroxylation
Section: 9.12
(Z)-3-methyl-3-hexene and catalytic OsO4 NMO.
Ans:
The reaction takes place with syn stereospecificity, giving a racemic
Topic: Predicting Reaction Products: anti Dihydroxylation

Section: 9.12
(Z)-3-methyl-3-hexene and MCPBA, followed by acidic water.
Ans:
The reaction takes place with anti stereospecificity, giving a racemic
Topic: Predicting Reaction Products: Oxidative Cleavage

Section: 9.12
143. Predict the product(s) of the oxidation of 2,3,4-trimethyl-1,5-heptadiene upon

treatment with O3 followed by dimethylsulfide (DMS).
Ans:
Section: 9.14
144. A common problem in the acid catalyzed hydration of alkenes is the formation of
an ether byproduct. Explain the formation of the ether byproduct in relation to the
reaction below:
Ans:
Topic: Predicting Reaction Products: Halohydrin Formation and Stereospecificity

Section: 9.12
145. Identify the structure(s) of the expected major organic product(s) of the following
reaction. Draw the products in the expected chair conformations and include
regiochemical and/or stereochemical details as needed.
Ans:

stereospecificity. The starting material is shown as a single enatiomers,
and thus produces two diastereomers. The product containing the cis
fused rings is capable of a ring flip.
Section: 9.13
146. Starting with (2R,3R)-2-chloro-3,4-dimethylpentane, a) draw the expected major

product for each step, including regiochemical and stereochemical details when
needed. In addition, b) briefly explain the mechanistic rational for each
transformation.
i. t-BuOK/t-BuOH, heat
ii. MCPBA/CH2Cl2
iii. H3O+
Ans:
Hofmann elimination occurs upon heating with the bulky potassium tert-
butoxide base, through an E2 elimination. Epoxidation with MCPBA is
stereospecific (syn), giving a racemic (R,R & S,R) epoxide. Ring opening
of the epoxide under acidic conditions is regio- and stereospecific.
Section: 9.13
147. For the following transformation a) identify the starting material with correct
stereochemistry and b) provide a complete reaction mechanism, including
stereochemistry, to account for the product shown.
Ans:
Step 1 involves the epoxidation of the (E) alkene by MCPBA, showing

only the enantiomer leading given product. Acid catalyzed ring opening
of the epoxide would occur with regiospecific addition of MeOH to the 3°
carbon. Deprotonation by a general base (likely MeOH in this example)
provides the product, which upon  bond rotation has the same
conformation as the product given in the question.
Section: 9.13
148. Consider the information given below and identify the structure of the unknown
compound A, with a molecular formula of C8H14. Compound A reacts with
Br2/CCl4. Upon reaction with excess H2/Ni 1-ethyl-2-methylcyclopentane is
produced. Subjecting A to ozonolysis, the product shown below is produced as the
major organic product. Draw the correct structure of compound A, and provide a
brief and clear explanation relating the data provide with the structure selected.
Ans: A must be 3-ethyl-4-methylcyclopentene. This given data can be

explained as shown below:

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Chapter 9

Multiple Choice Questions:

Topic: Addition Reaction Mechanisms

1. In an addition reaction to an alkene, the π bond plays the role of:

Topic: Addition Reaction Mechanisms

2. Addition reactions of alkenes are characterized by:

Topic: Addition vs. Elimination Thermodynamic Perspective

4. In a reaction where addition and elimination reactions are in competition, which of

Topic: Addition vs. Elimination Thermodynamic Perspective

5. Which statement is true about the temperature dependence of an addition reaction?

Topic: Addition vs. Elimination Thermodynamic Perspective

7. Addition reactions are favorable at low temperatures because:

8. Which of the molecules below would be the expected product for

9. In the addition reaction of HI to 2-methyl-2-butene, the Markovnikov addition

10. The expected Markovnikov addition product of HI to 2-methyl-2-butene is:

11. The regioselectivity and stereospecificity in hydrohalogenation of an alkene is best

13. What compound is the expected product upon Markovnikov hydrohalogenation

14. The expected major product of the following reaction is:

15. The expected major product of the following reaction is:

17. Which of the molecules below arises from anti-Markovnikov hydrohalogenation

Topic: Stereochemistry of Hydrohalogenation

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

Topic: Stereochemistry of Hydrohalogenation

Topic: Stereochemistry of Hydrohalogenation

23. Which of the following carbocations is likely to undergo rearrangement through a

Topic: Hydrohalogenation and Carbocation Rearrangements

24. Which of the following carbocations is likely to undergo rearrangement through a

Topic: Hydrohalogenation and Carbocation Rearrangements

Topic: Hydrohalogenation and Carbocation Rearrangements

29. Select the expected major product(s) of the following reaction:

Topic: Hydrohalogenation and Carbocation Rearrangements

31. The regioselectivity and stereospecificity in the acid-catalyzed hydration of an

Topic: Acid Catalyzed Hydration

32. The expected major product of the following reaction is:

33. The expected major product of the following reaction is:

Topic: Acid Catalyzed Hydration

34. The expected major product of the following reaction is:

35. Treatment of 1-methylcyclohexene with H3O+ would be expected to yield as the

Topic: Acid Catalyzed Hydration

36. Treatment of (S)-6-chloro-1-methyl-1-cyclohexene with H3O+ is expected to

38. The regioselectivity and stereospecificity in the oxymercuration-demercuration of

40. What synthetic goal is achieved by subjecting an alkene to an oxymercuration-

44. When an alkene is subjected to treatment with Hg(OAc) 2 in alcohol, followed by

45. The regioselectivity and stereospecificity in the hydroboration-oxidation of an

46. What reagents are needed to accomplish the following transformation?

Topic: Catalytic Hydrogenation

Topic: Catalytic Hydrogenation

54. What product is formed when 5-chloro-1-methylcyclohexene is reduced with a Pt

55. What product is formed when trans-1,2-dimethylcyclohexane is reacted with Pd/C

Topic: Catalytic Hydrogenation

Topic: Catalytic Hydrogenation

58. Which alkene would yield 3-methylpentane upon subjection to catalytic

Topic: Catalytic Hydrogenation

Topic: Catalytic Hydrogenation

Topic: Catalytic Hydrogenation

62. In conducting a catalytic hydrogenation of an alkene, which catalyst listed is most

Topic: Catalytic Hydrogenation

63. Wilkinson’s catalyst accomplishes which of the listed molecular transformations?

Topic: Catalytic Hydrogenation

Topic: Catalytic Hydrogenation

66. For the complete reduction of 1 mole of (3E,5E)-hepta-1,3,5-triene with H2 using a

67. What products are produced from the reaction below?

Topic: Catalytic Hydrogenation and Stereospecificity

Topic: Halogenation and Stereospecificity

71. Treating 2-methyl-2-pentene with Br2 is expected to produce which of the

72. The expected intermediate formed during a halohydrin reaction is: