Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

Chapter 12: Reactions of Arenes - Electrophilic Aromatic

Substitution

1. What is the product of the following reaction?

A) isobutylbenzene
B) 2-methyl-1-phenylpropene
Ans: D

C)
D)

sec-butylbenzene
tert-butylbenzene

2. The major product(s) in the nitration of benzoic acid is(are)

A) mixture of ortho and para-nitrobenzoic acid.
B) nitrobenzene.
C) meta-nitrobenzoic acid.
D) nitrobenzene and para-nitrobenzoic acid.
Ans: C
3. Which of the following aromatic compounds reacts faster than benzene in electrophilic
aromatic bromination?

A) A B) B C) C D) D
Ans: C
4. Nitration of benzoic acid has a reaction rate which is __________ than the nitration rate
of benzene and gives primarily the _____________ product(s).
A) slower, meta
C) faster, ortho,para
B) slower, ortho,para
D) faster, meta
Ans: A

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

5. Which one of the following is the electrophile in the reaction shown below?

A) benzene B) NO3
Ans: C

C) NO2+

D) H2SO4

6. What is the electrophile in the Friedel-Crafts alkylation reaction below?

A) AlCl3
Ans: D

B) Cl

C) benzene

D) (CH3)3C+

7. Which point on the potential energy diagram corresponds to the species shown to the
right for the electrophilic bromination of benzene with Br2/FeBr3?

A) A B) B C) C D) D
Ans: B
8. Which species below best depicts the electrophile in the FeBr3-catalyzed bromination of
benzene?
A) Br2 B) FeBr4Ans: C

C)

D) FeBr3

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

9. Which one of the following reactions does not give tert-butylbenzene?

A) benzene + (CH3)3CCl/AlCl3
C) benzene + (CH3)3CH/AlCl3
B) benzene + (CH3)2C=CH2/H2SO4
D) benzene + (CH3)3COH/H2SO4
Ans: C
10. Which point on the potential energy diagram corresponds to the species shown to the
right for the electrophilic nitration of benzene with HNO3/H2SO4?

A) A B) B C) C D) D
Ans: C
11. What is(are) the product(s) of the following reaction?

A)
B)
C)
D)
Ans:

C6H5CH2CH2CH3
C6H5CH(CH3)2
C6H5CH2CH2CH2C1
a mixture of C6H5CH2CH2CH3 and C6H5CH(CH3)2
D

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

12. Which one of the following is not a resonance form of the cyclohexadienyl cation
intermediate in the bromination of benzene?

A) A B) B C) C D) D
Ans: B
13. How many mononitration products are possible in the nitration of naphthalene, shown
below?

A) only 1
Ans: B

B) 2

C) 3

D) 4

14. Rank the following compounds in order of decreasing reactivity to aromatic

electrophilic bromination.
I. benzene II. toluene III. benzoic acid IV. phenol
A) IV > II > I > III
C) II > I > IV > III
B) IV > III > II > I
D) II > III > IV > I
Ans: A
15. Which of the following groups are ortho/para directors?
I. NO2 II. OCH3 III. CO2CH3 IV. CH3
A) I and III B) II and III C) II and IV D) III and IV
Ans: C

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

16. Predict the effect the substituent attached to the benzene ring below would have on
electrophilic aromatic substitution reactions?

A) ortho/para director, activator

B) ortho/para director, deactivator
Ans: D

C)
D)

meta director, activator

meta director, deactivator

17. In the Friedel-Crafts alkylation of benzene, dialkylation is often a significant byproduct. In the Friedel-Crafts acylation of benzene, diacylation is not a significant byproduct. Which of the following is the primary reason for this difference?
A) Alkyl groups activate the ring to further substitution, acyl groups deactivate it.
B) Alkyl groups are less sterically hindered than acyl groups.
C) Acyl cations are more difficult to make with Lewis acids.
D) Unlike acyl cations, carbocations can undergo rearrangements.
Ans: A
18. Which of the following is the best method to make n-butylbenzene?

A) A B) B C) C D) D
Ans: C

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

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

A) 4-ethyl-2-nitrophenol
B) 4-ethyl-3-nitrophneol
Ans: A

C)
D)

1-ethyl-4-nitrobenzene
4-nitrophenol

20. Based on resonance theory, what is the approximate charge on the indicated carbon?

A) +1 B) +0.50
Ans: C

C) +0.33

D) +0.20

21. Which isomer of dichlorobenzene gives a single mononitration product?

A) ortho B) meta C) para D) none of them
Ans: C
22. Arrange the following compounds in order of increasing reaction rate with
HNO3/H2SO4.
I. C6H5CH=O II. C6H5OCH3 III. C6H5Br IV. C6H5CH3
A) I < III < IV < II
C) III < I < II < IV
B) I < IV < III < II
D) III < I < IV < II
Ans: A

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

23. Salicylic acid reacts with two equivalents of ICl to give one of the products below.
Which one is it? (Hint: Cl is more electronegative than I.)

A) A B) B C) C D) D
Ans: D
24. Identify the preferred site(s) of electrophilic attack on the following compound.

A) ortho/para positions on ring 1

B) meta position on ring 1
Ans: C

C)
D)

ortho/para positions on ring 2

meta position on ring 2

25. Which of the following is the best method to make meta-bromoethylbenzene from
benzene?

A) A B) B C) C D) D
Ans: D

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

26. Which one of the following compounds undergoes electrophilic aromatic sulfonation at
the fastest rate?

A) A B) B C) C D) D
Ans: D
27. What is the product of the following series of reactions?

A) A B) B C) C D) D
Ans: B

Page 8
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

28. Nitration of chlorobenzene has a reaction rate which is __________ than the nitration
rate of benzene and gives primarily the _____________ product(s).
A) faster, ortho/para B) faster, meta C) slower, ortho/para D) slower, meta
Ans: C
29. What is the major product of the Friedel-Crafts alkylation of benzene with
(CH3)2CHCH2Cl and AlCl3?
A) isobutylbenzene
C) sec-butylbenzene
B) tert-butylbenzene
D) butylbenzene
Ans: B
30. Where would the compound shown below undergo bromination with Br2/FeBr3?

A) ortho/para position on ring 1

B) meta position on ring 1
Ans: A

C)
D)

ortho/para position on ring 2

meta position on ring 2

31. Where would the compound shown below undergo bromination with NBS and benzoyl
peroxide?

A) ortho/para position on ring 1

B) meta position on ring 1
Ans: D

C)
D)

C(2) position on ring 2

methyl group on ring 2

Page 9
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

32. Based on directing effects in electrophilic aromatic substitution reactions, predict the
major addition product of the following reaction.

A) A B) B C) C D) D
Ans: B
33. Which one of the following substituents is deactivating and ortho-para directing in
electrophilic aromatic substitution reactions?
A) Cl B) N(CH3)2 C) CO2H D) CH=CH2
Ans: A
34. Consider the partial rate factors for electrophilic aromatic substitution at the indicated
position of anisole and nitrobenzene. Which of the following correlates to these partial
rate factors?

A) A B) B C) C D) D
Ans: B

Page 10
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

35. Starting with toluene, which of the following is the best synthesis of metabromobenzoic acid?

A) A B) B C) C D) D
Ans: C
36. Predict which position of the naphthalene compound below is the most reactive with
electrophiles in electrophilic aromatic substitution?

A) A B) B C) C D) D
Ans: D

Page 11
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

37. Starting with toluene, which of the following is the best method to make the ether
shown below? (Assume you can separate ortho and para isomers.)

A) A B) B C) C D) D
Ans: B
38. Identify the major product(s) of the reaction sequence shown below.

A) ortho and para-chloroacetophenone

B) meta-chloroacetophenone
Ans: B

C)
D)

ortho and para-chlorobenzaldehyde

meta-chlorobenzaldehyde

Page 12
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

39. Which of the following is not a valid resonance form of the intermediate species in the
reaction shown below?

A) A B) B C) C D) D
Ans: A
40. How many mononitration products are possible in the nitration of the compound shown
below?

A) only 1
Ans: B

B) 2

C) 3

D) 4

Page 13
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

41. What is the product of the following reaction?

A) A B) B C) C D) D
Ans: C
42. What is the product of the following reaction?

A) benzene B) ortho-chloroaniline C) meta-chloroaniline

Ans: D

D) aniline

Page 14
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

43. Which one of the following has the weakest carbon-chlorine bond?

A) I B) II
Ans: A

C) III

D) IV

44. Which compound in each of the following pairs is the most reactive to the conditions
indicated?

A) I and III
Ans: A

B) I and IV

C) II and III

D) II and IV

45. Which of the following reacts at the fastest rate with potassium methoxide (KOCH3) in
methanol?
A) fluorobenzene
C) 2,4-dinitrofluorobenzene
B) 4-nitrofluorobenzene
D) 2,4,6-trinitrofluorobenzene
Ans: D
46. Which of the following reacts at the fastest rate with potassium methoxide (KOCH3) in
methanol?
A) fluorobenzene
C) p-fluorotoluene
B) p-nitrofluorobenzene
D) p-bromofluorobenzene
Ans: B

Page 15
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

47. Which of the following is the kinetic rate equation for the addition-elimination
mechanism of nucleophilic aromatic substitution?
A) rate = k[aryl halide]
C) rate = k[aryl halide][nucleophile]
B) rate = k[nucleophile]
D) rate = k[aryl halide][nucleophile]2
Ans: C
48. Which of the following is not a resonance form of the intermediate in the nucleophilic
addition of hydroxide ion to para-fluoronitrobenzene?

A) I B) II
Ans: C

C) III

D) IV

49. Which chlorine is most susceptible to nucleophilic substitution with NaOCH3 in

methanol?

A) #1
B) #2
Ans: B

C)
D)

#1 and #2 are equally susceptible.

No substitution is possible.

50. What is the product of the following reaction?

A) N,N-dimethylaniline
B) para-chloro-N,N-dimethylaniline
Ans: A

C)
D)

phenyllithium (C6H5Li)
meta-chloro-N,N-dimethylaniline

Page 16
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

51. Which one of the reagents readily reacts with bromobenzene without heating?
A) NaOCH2CH3 B) NaCN/DMSO C) NaNH2/NH3 D) (CH3)2NH
Ans: C
52. Which of the following would work best for the synthesis of the ether shown below?

A) A B) B C) C D) D
Ans: C

Page 17
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

53. Carbon-14 labelled chlorobenzene is reacted with sodium amide in ammonia as shown
below. Which of the following depicts the carbon-14 labeled in the product(s)?

A) A B) B C) C D) D
Ans: C

Page 18
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

54. Identify the product(s) of the following reaction.

A)
B)
C)
D)
Ans:

only ortho-methylaniline
ortho-methylaniline and meta-methyaniline
meta-methylaniline and para-methyaniline
ortho-methylaniline and para-methyaniline
B

55. Which of the following best estimates the percentages of the three isomeric
methylanilines from the reaction shown below?

A) A B) B C) C D) D
Ans: C

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

56. Which of the following is a key intermediate in the reaction shown below?

A) I B) II
Ans: A

C) III

D) IV

Page 20
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

57. Identify the diene required for the synthesis shown below.

A) A B) B C) C D) D
Ans: A
58. Assume that the following reaction goes by the elimination-addition mechanism for
nucleophilic aromatic substitution. Based on that, how many isomeric naphthylamines
are expected in the following reaction?

A) only a single product

Ans: C

B) two

C) three D) four

Page 21
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

59. Which of the following best estimates the percentages of the three isomeric deuterated
anilines from the reaction shown below?

A) A B) B C) C D) D
Ans: A
60. Which of the following is(are) true concerning the intermediate benzyne?
I. Benzyne is aromatic.
II. All the hydrogens of benzyne are equivalent and indistinguishable.
III. The benzyne molecule has strain energy.
A) only I B) only III C) I and III D) II and III
Ans: C

Page 22
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

61. Which of the following is(are) true concerning the intermediate in the additionelimination mechanism of the reaction below?

I. The intermediate is aromatic.

II. The intermediate is a resonance stabilized anion.
III. Electron withdrawing groups on the benzene ring stabilize the intermediate.
A) only I B) only II C) I and III D) II and III
Ans: D
62. Which one of the following has the fastest rate of reaction with sodium ethoxide,
NaOCH2CH3, at 25C?
A) para-fluoronitrobenzene
C) para-bromonitrobenzene
B) para-chloronitrobenzene
D) para-iodonitrobenzene
Ans: A
63. Arrange the following compounds in order of increasing reactivity with sodium
methoxide, NaOCH3?

A) I < II < III

Ans: B

B) I < III < II

C) II < I < III D) III < II < I

Page 23
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

64. Which position on the potential energy diagram corresponds to the species shown for
the reaction of para-fluoro (trifluoromethyl) benzene with sodium methoxide?

A) A B) B C) C D) D
Ans: C

Page 24
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

65. Which of the following is the product from the reaction sequence shown below?

A) A B) B C) C D) D
Ans: A

Page 25
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

66. Identify the likely mechanism in the reaction shown below.

A) SN2
B) SN1
Ans: D

C)
D)

electrophilic addition-elimination
nucleophilic addition-elimination

67. Which of the following is NOT a common electrophile in electrophilic aromatic

substitution reactions?
A) +SO3H B) +Br C) +CN D) +NO2
Ans: C
68. Ranked in order of decreasing reactivity in electrophilic aromatic substitution reactions,
the order would be (more reactive > less reactive)
A) chlorobenzene > toluene > acetophenone
B) chlorobenzene > acetophenone > toluene
C) toluene > chlorobenzene > acetophenone
D) toluene > acetophenone > chlorobenzene
Ans: C
69. Which statement is true in electrophilic aromatic substitution?
A) no meta directors have a nitrogen atom directly attached to the ring
B) all ortho/para directors make the ring more reactive than benzene
C) no meta directors have non-bonding electrons on the atom directly attached to the
ring
D) all ortho/para directors have non-bonding electrons on the atom directly attached
to the ring
Ans: C

Page 26
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

70. What would be the most efficient way to make meta-nitrobromobenzene?

A)
B)
C)
D)
Ans:

bromobenzene + HNO3/H2SO4
nitrobenzene + Br2/FeBr3
either of these approaches would work
neither of these approaches would work
B

71. Which one of the common electrophilic aromatic substitution reactions puts an electron
donating group on a benzene ring?
A) Br2, FeBr3 B) SO3 + H2SO4 C) RCOCl + AlCl3 D) RCl + AlCl3
Ans: D
72. What major product do you expect?

A) A B) B C) C D) D
Ans: D

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Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

73. How many TOTAL resonance structures can be drawn for this intermediate? (incl. this
one)

A) one B) two
Ans: D

C) three

D) four

74. Of the choices given, where would an aromatic substitution occur on this molecule?

A) A B) B C) C D) D
Ans: B
75. What major product(s) would you expect from this reaction?

A) A B) B C) C D) D
Ans: C
Page 28
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.

Chapter 12 Reactions of Arenes - Electrophilic Aromatic Substitution: Answers

Prof. Sivaguru Jayaraman

76. How would you best accomplish this?

A)
B)
C)
D)
Ans:

1. SO3, H2SO4, heat; 2. K2Cr2O7, H2SO4

1. K2Cr2O7, H2SO4, heat; 2. SO3, H2SO4
either of these would work.
neither of these would work.
B

Page 29
Chem 341: Organic Chemistry, Prof. Sivaguru Jayaraman, Fall 2010.