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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
Difficulty Level: Easy

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

Topic: Addition vs. Elimination Thermodynamic Perspective


Section: 9.2
Difficulty Level: Easy

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

Topic: Addition vs. Elimination Thermodynamic Perspective


Section: 9.2
Difficulty Level: Easy

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
Topic: Addition vs. Elimination Thermodynamic Perspective
Section: 9.2
Difficulty Level: Moderate

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

Topic: Addition vs. Elimination Thermodynamic Perspective


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
Difficulty Level: Easy

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


hydrohalogenation of the following alkene:

A)

B)
C)

D)

E)
Ans: E

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

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

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

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
Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

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

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

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
Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

13. What compound is the expected product upon Markovnikov hydrohalogenation


with HBr of the alkene shown below?

A)

B)

C)

D)

E)
Ans: B

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

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

A)

B)

C)

D)

E)
Ans: C
Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

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

A)

B)

C)

D)

E)
Ans: A

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

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
Difficulty Level: Easy

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
Difficulty Level: Easy

18. Which of the alkenes shown below would produce a chirality center upon
hydrohalogenation?

A)

B)

C)

D)
E)
Ans: B
Topic: Stereochemistry of Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

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

A)

B)

C)

D)

E)
Ans: A

Topic: Stereochemistry of Hydrohalogenation


Section: 9.3
Difficulty Level: Moderate

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
Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Moderate

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

Topic: Stereochemistry of Hydrohalogenation


Section: 9.3
Difficulty Level: Moderate

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
Difficulty Level: Moderate

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

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate

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
Topic: Hydrohalogenation and Carbocation Rearrangements
Section: 9.3
Difficulty Level: Moderate

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

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate

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
Difficulty Level: Moderate

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

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Hard

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
Topic: Hydrohalogenation and Carbocation Rearrangements
Section: 9.3
Difficulty Level: Hard

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

A)

B)

C)
D) A and B
E) A and C
Ans: C

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Hard

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
Difficulty Level: Easy

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

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy

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

A) I
B) II
C) III
D) IV
E) V
Ans: D
Topic: Acid Catalyzed Hydration
Section: 9.4
Difficulty Level: Easy

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

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

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy

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

A)

B)

C)

D)

E)
Ans: D
Topic: Acid Catalyzed Hydration
Section: 9.4
Difficulty Level: Easy

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

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Moderate

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
Topic: Acid Catalyzed Hydration
Section: 9.4
Difficulty Level: Hard

37. What is the expected major product for the following reaction?

A)

B)

C)

D)

E)
Ans: A
Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy

38. The regioselectivity and stereospecificity in the oxymercuration-demercuration 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: B

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy

39. What is the expected major product for the following reaction?

A)

B)

C)

D)

E)
Ans: B
Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy

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

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy

41. What is the expected major product for the following reaction?

A)

B)

C)

D)

E)
Ans: C
Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy

42. What is the expected major product for the following reaction?

A)

B)

C)

D)

E)
Ans: D
Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy

43. What is the expected major product for the following reaction?

A)

B)

C)

D)

E)
Ans: B

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Moderate

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
Difficulty Level: Easy

45. The regioselectivity and stereospecificity in the hydroboration-oxidation 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) Markovnikov orientation with both syn- and anti-addition
Ans: C

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy

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
Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy

47. What is the expected major product for the following reaction sequence?

A)

B)

C)

D)

E)
Ans: E

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy

48. What is the expected major product for the following reaction sequence?

A) I
B) II
C) III
D) I and II
E) I and III
Ans: E
Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Moderate

49. What is the expected major product for the following reaction sequence?

A)

B)

C)

D)

E)
Ans: E
Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Moderate

50. What is the expected major product for the following reaction sequence?

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

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Moderate

51. What is the expected major product for the following reaction sequence?

A)

B)

C)

D)

E)
Ans: B
Topic: Catalytic Hydrogenation
Section: 9.7
Difficulty Level: Easy

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

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy

53. Provide the major organic product(s) for the reaction shown below.

A)

B)

C)

D)

E)
Ans: B

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy

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
Topic: Catalytic Hydrogenation
Section: 9.7
Difficulty Level: Easy

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
E) None of the above
Ans: A

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy

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

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy

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
Topic: Catalytic Hydrogenation
Section: 9.7
Difficulty Level: Easy

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


hydrogenation?

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

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy

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
E) None of the above
Ans: B

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy

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
Topic: Catalytic Hydrogenation
Section: 9.7
Difficulty Level: Easy

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

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy

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

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy

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
Topic: Catalytic Hydrogenation
Section: 9.7
Difficulty Level: Easy

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

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Moderate

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

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Moderate

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
Difficulty Level: Moderate

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
Difficulty Level: Moderate

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
Difficulty Level: Easy

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
Difficulty Level: Easy

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
Difficulty Level: Easy

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
Difficulty Level: Easy

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

Topic: Halohydrin Formation


Section: 9.8
Difficulty Level: Easy

73. What major product is expected from the following reaction?

A) I
B) II
C) III
D) IV
E) V
Ans: D
Topic: Halohydrin Formation
Section: 9.8
Difficulty Level: Moderate

74. What is the expected major product for the following reaction?

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

Topic: Halogenation and Stereospecificity


Section: 9.8
Difficulty Level: Moderate

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
Topic: Halogenation and Stereospecificity
Section: 9.8
Difficulty Level: Moderate

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
Difficulty Level: Hard

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
Difficulty Level: Easy

78. For the reaction sequence below, identify the expected major products.

A)

B)

C)

D)

E)
Ans: B

Topic: anti dihydroxylation


Section: 9.9
Difficulty Level: Moderate

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
Topic: anti dihydroxylation
Section: 9.9
Difficulty Level: Moderate

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

Topic: anti dihydroxylation


Section: 9.9
Difficulty Level: Moderate

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

A) I
B) II
C) III
D) IV
E) V
Ans: D
Topic: anti dihydroxylation
Section: 9.9
Difficulty Level: Hard

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

Topic: anti dihydroxylation


Section: 9.9
Difficulty Level: Hard

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
Difficulty Level: Easy

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

Topic: syn Dihydroxylation


Section: 9.10
Difficulty Level: Easy

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
Topic: syn Dihydroxylation
Section: 9.10
Difficulty Level: Easy

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

Topic: syn Dihydroxylation


Section: 9.10
Difficulty Level: Easy

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
Topic: syn Dihydroxylation
Section: 9.10
Difficulty Level: Easy

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

A)

B)

C)

D)
E) None of the above
Ans: A

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Easy

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
Topic: Oxidative Cleavage
Section: 9.11
Difficulty Level: Easy

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

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Moderate

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
Topic: Oxidative Cleavage
Section: 9.11
Difficulty Level: Moderate

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

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Moderate

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
Topic: Oxidative Cleavage
Section: 9.11
Difficulty Level: Moderate

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
Difficulty Level: Easy

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

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Easy

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

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Easy

97. What is the expected major product for the following reaction sequence?

A)

B)

C)

D)

E)
Ans: A
Topic: Predicting Addition Products
Section: 9.12
Difficulty Level: Easy

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

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Easy

99. Which reaction is not stereospecific?

A) I
B) II
C) III
D) IV
E) V
Ans: C
Topic: Predicting Addition Products
Section: 9.12
Difficulty Level: Moderate

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

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Moderate

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
Topic: Predicting Addition Products
Section: 9.12
Difficulty Level: Moderate

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

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Hard

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
Difficulty Level: Easy

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

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Easy

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
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Easy

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

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Easy

107. What is the expected major product of the following reaction sequence?

A) I
B) II
C) III
D) IV
E) V
Ans: C
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Moderate

108. What is the expected major product of the following reaction sequence?

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

Topic: Synthetic Strategies, anti Dihydroxylation


Section: 9.13, 9.9
Difficulty Level: Moderate

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
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Moderate

110. What is the expected major product of the following reaction sequence?

A) I
B) II
C) III
D) IV
E) V
Ans: C
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Moderate

111. What is the expected major product of the following reaction sequence?

A)

B)

C)

D)

E)
Ans: A
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Moderate

112. What is the expected major product for the following reaction?

A)

B)

C)

D)

E)
Ans: A
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Moderate

113. What is the expected major product of the following reaction sequence?

A)

B)

C)

D)

E)
Ans: C
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Moderate

114. What is the expected major product of the following reaction sequence?

A)

B)

C)

D)

E)
Ans: A
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Hard

115. What is the expected major product of the following reaction sequence?

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

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard

116. For the following reaction sequence, which molecule is an expected major product?

A)

B)

C)

D)

E)
Ans: A
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Hard

117. What is the expected major product of the following reaction sequence?

A)

B)

C)

D)

E)
Ans: E
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Hard

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

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard

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
Difficulty Level: Easy

120.  bonds are quite susceptible to reaction with electron-seeking reagents, also
referred to as ____________________.
Ans: electrophiles

Topic: Regioselectivity
Section: 9.3
Difficulty Level: Easy

121. The rule that correctly predicts the regiochemistry of most ionic additions to
alkenes is called ____________________.
Ans: Markovnikov's Rule

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

122. For the following reaction sequence provide the expected major organic product(s).
Include all stereoisomers showing relevant stereochemistry.

Ans:

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy

123. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:

Ans:
Topic: Hydrohalogenation and Carbocation Rearrangements
Section: 9.3
Difficulty Level: Moderate

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.

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate

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.
Topic: Hydrohalogenation and Carbocation Rearrangements
Section: 9.3
Difficulty Level: Moderate

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
Difficulty Level: Easy

127. For the following reaction sequence provide the expected major organic product(s).
Include all stereoisomers showing relevant stereochemistry.

Ans:

Topic: Acid-Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy

128. For the following reaction sequence provide the expected major organic product(s).
Include all stereoisomers and clearly show relevant stereochemistry.

Ans:

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy

129. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:

Ans:
Topic: Acid-Catalyzed Hydration
Section: 9.4
Difficulty Level: Moderate

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.

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy

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

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy

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


Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy

133. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:

Ans:

Topic: Halohydrin Formation


Section: 9.8
Difficulty Level: Easy

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.

Topic: Halohydrin Formation


Section: 9.8
Difficulty Level: Moderate

135. For the following transformation below, provide a detailed step-wise mechanism
showing the electron flow using the curved arrow formalism.

Ans:
Topic: Halohydrin Formation
Section: 9.8
Difficulty Level: Moderate

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.

Topic: Halogenation and Stereospecificity


Section: 9.8
Difficulty Level: Moderate

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.
Topic: Oxidative Cleavage
Section: 9.11
Difficulty Level: Easy

138. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:

Ans:

and

Topic: Predicting Reaction Products: Halohydrin Formation and Stereospecificity


Section: 9.12
Difficulty Level: Moderate

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:
The reaction takes place with Markovnikov regioselectivity and anti
stereospecificity. As the product is chiral, the products are diastereomers.

Topic: Predicting Reaction Products: syn Dihydroxylation


Section: 9.12
Difficulty Level: Moderate

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
Difficulty Level: Moderate

141. Draw Fischer projection formula(s) of the major product(s) of the reaction between
(Z)-3-methyl-3-hexene and catalytic OsO4 NMO.

Ans:
The reaction takes place with syn stereospecificity, giving a racemic
mixture of the diol product.

Topic: Predicting Reaction Products: anti Dihydroxylation


Section: 9.12
Difficulty Level: Moderate

142. Draw Fischer projection formula(s) of the major product(s) of the reaction between
(Z)-3-methyl-3-hexene and MCPBA, followed by acidic water.

Ans:
The reaction takes place with anti stereospecificity, giving a racemic
mixture of the diol product.

Topic: Predicting Reaction Products: Oxidative Cleavage


Section: 9.12
Difficulty Level: Moderate

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:
Topic: Synthetic Strategies
Section: 9.14
Difficulty Level: Moderate

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
Difficulty Level: Hard

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:

The reaction takes place with Markovnikov regioselectivity and anti


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.
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Hard

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.
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Hard

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.
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Hard

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: