Practice Problems For Chapter 15 With Answers (2) 2

Chapter 15
MULTIPLE CHOICE QUESTIONS
Topic: Reaction Products
1. The major product(s), A, of the following reaction,
Cl2, h
CH3CH2 A
400 - 600 oC
CH3CH2 Cl CH3CH2 ClCH2CH2 CH3CH

Cl Cl
I II III IV
would be:
A) I
B) II
C) A mixture of I and II
D) III
E) IV
Ans: E
2. What would be the major product(s) of the following reaction?
CO2H
HNO3 ?
NO2 H2SO4, heat
CO2H
CO2H CO2H CO2H
NO2 O2N
NO2
NO2 O2N NO2 NO2
NO2
I II III IV
A) I
B) II
C) III
D) IV
E) Equal amounts of II and IV
Ans: C
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Chapter 15
3. The major product(s), C, of the following reaction,
Cl
SO3
C
Cl H2SO4
Cl Cl Cl
SO3H
Cl Cl HO3S Cl
SO3H
I II III
would be:
A) I
B) II
C) III
D) Equal amounts of I and II
E) Equal amounts of I and III
Ans: B
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Chapter 15
4. The major product(s), D, of the following reaction,
O
Br2
C CH2 D
FeBr3
O O
Br C CH2 C CH2
Br
I II
O O
C CH2 C CH2 Br
Br
III IV
would be:
A) I
B) II
C) III
D) IV
E) Equal amounts of I and II
Ans: D
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Chapter 15
5. What would be the product of the following reaction sequence?

OH i) SOCl2
?
O ii) C6H6, AlCl3
iii) Zn(Hg), HCl, heat
O O OH
OH
I II III
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: E
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Chapter 15
6. What would you expect to be the major product obtained from the following reaction?
COOH
Br2
?
SO3H FeBr3
COOH COOH COOH COOH

Br Br
SO3H SO3H Br SO3H SO3H

Br
I II III IV
A) I
B) II
C) III
D) IV
Ans: C
7. What would be the major product of the following reaction?
Cl2
CH2CH2CH3 ?
400 oC
Cl CH2CH2CH3 CH2CH2CH3 CHCH2CH3

Cl Cl
I II III
CH2CHCH3 CH2CH2CH2Cl
Cl
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: C
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Chapter 15
NO2
Br2
?
SO3H FeBr3
NO2 NO2 NO2 NO2

Br Br
SO3H SO3H Br SO3H SO3H

Br
I II III IV
A) I
B) II
C) III
D) IV
Ans: C
O
HNO3
HN
?
H2SO4, heat
NO2
O O O
O2N
HN HN HN
O2N
I II III
O O
HN HN NO2
NO2
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: E
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Chapter 15
10. What would be the major product(s) of the following reaction?
O
H2SO4 ?
NO2
O
O O O
SO3H HO3S
NO2
NO2 HO3S NO2 NO2
SO3H
I II III IV
A) I
B) II
C) III
D) Equal amounts of IV
Ans: C
11. What would you expect to be the major product obtained from the mononitration of m-
dichlorobenzene?
Cl
Cl Cl
NO2
Cl
Cl O2N Cl
NO2
I II III
A) I
B) II
C) III
D) Equal amounts of I and II
E) Equal amounts of I, II and III
Ans: B
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Chapter 15
HO O
HNO3
?
SO3H
H2SO4 , heat
HO O
HO O HO O HO O
NO2 O2N
SO3H
SO3H O2N SO3H SO3H
NO2
I II III IV
A) I
B) II
C) III
D) IV
Ans: C
533
Chapter 15
13. What product would result from the following series of reactions,
i) AlCl3
Cl ii) N-Bromosuccinimide, peroxides
+ ?
iii) CH3ONa, CH3OH, heat
iv) MMPP
v) CH3MgBr
vi) NH4Cl
Br
HO
HO
I II III
HO
HO
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: D
534
Chapter 15
14. The major product(s), D, of the following reaction
O HNO3
D
H2SO4
O O
O2N
I NO2 II
NO2
O O
NO2
III IV
would be:
A) I
B) II
C) III
D) IV
Ans: D
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Chapter 15
15. What would be the major product of the following reaction?

NBS, ROOR ?
light
Br
Br
Br
I II III
Br
Br
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: C
16. Which would be the major product(s) of the following reaction?

HO O
HNO3
?
H2SO4
HO O HO O HO O
NO2
NO2 HO3S
I II III
A) I
B) II
C) III
D) I and II in roughly equal amounts
E) I and III in roughly equal amounts
Ans: A
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Chapter 15
17. Which would be the product, X, of the following reaction sequence?

O i) SOCl2
?
OH ii) benzene, AlCl3
iii) Zn(Hg), HCl
SO2 CO2 CH2
I II III
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: C
537
Chapter 15
18. Toluene is subjected to the action of the following reagents in the order given: (1)
KMnO4,OH-, heat; then H3O+ (2) HNO3, H2SO4 (3) Br2, FeBr3
What is the final product of this sequence?
CO2H CO2H CO2H
NO2
Br NO2 Br
NO2 Br
I II III
Br
CH3
Br NO2
NO2 CO2H
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: A
19. When toluene is reacted in turn with 1) Cl2 (large excess), heat, and light and 2)
Br2,FeBr3, the chief product is:
Br
CCl3 CCl3 CCl3
Br
Br
Cl Br
I II III IV
A) I
B) II
C) III
D) IV
E) A mixture of III and IV
Ans: B
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Chapter 15
20. The reaction of benzene with (CH3)3CCH2Cl in the presence of anhydrous aluminum
chloride produces principally which of these?
I II III
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: E
21. What might be predicted to happen when the following substance undergoes Friedel-
Crafts acylation?
O2N CH2
A B
A) Substitution occurs in ring B, p- to the methylene group
B) Substitution occurs in ring A, o- to the nitro group
C) Substitution occurs in ring A, o- to the methylene group
D) Substitution occurs in ring B, m- to the methylene group
E) None of the above. No reaction will occur.
Ans: A
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Chapter 15
Topic: Nomenclature, Reaction Products
22. A mixture of chlorobenzene (1 mol) and acetanilide (1mol) is allowed to react with Br2
(0.5 mol) in the presence of trace amounts of FeBr3. What is the principal product of
the competing reactions?
A) 1-bromo-4-chlorobenzene
B) 1-bromo-2-chlorobenzene
C) 1-bromo-3-chlorobenzene
D) 4-bromoacetanilide
E) 3-bromoacetanilide
Ans: D
Topic: Nomenclature, Reaction Products
23. What is the chief product of the Friedel-Crafts alkylation of benzene with 1-butene and
AlCl3?
A) butylbenzene
B) 2-phenylbutane
C) 2-methyl-1-phenylpropane
D) t-butylbenzene
E) 2,2-diphenylbutane
Ans: B
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Chapter 15
24. Which of the following reactions would give the product(s) indicated in substantial
amounts (i.e., in greater than 50% yield)?
NH2 NH2 NH2

AlCl3 CH3
I + CH3Cl and
CH3
NH2 NH2
AlCl3
II + CH3Cl
CH3
AlCl3 CH2CH2CH3
III + CH3CH2CH2Cl
A) I
B) II
C) III
D) All of these
E) None of these
Ans: E
Topic: Reagents
25. Which reagent(s) would you use to carry out the following transformation?
toluene  benzoic acid
A) Br2, heat, and light
B) Cl2, FeCl3
C) KMnO4, OH-, heat (then H3O+)
D) HNO3/H2SO4
E) SO3/H2SO4
Ans: C
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Chapter 15
Topic: Reagents
ethylbenzene  1-chloro-1-phenylethane
A) Cl2, light, and heat
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E) HCl, O2
Ans: A
Topic: Reagents
isopropylbenzene  2- and 4-chloro-1-isopropylbenzene
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E) HCl, peroxides
Ans: B
Topic: Reagents
28. Which reagent would you use to carry out the following transformation?
tert-butylbenzene  p-tert-butylbenzenesulfonic acid
+
o-tert-butylbenzenesulfonic acid
A) HNO3/H2SO4
B) tert-C4H9Cl/AlCl3
C) H2SO3/peroxides
D) SO3/H2SO4
E) SO2/H2SO3
Ans: D
Topic: Reagents
ethylbenzene  benzoic acid
B) Cl2, FeCl3
C) KMnO4, OH-, heat (then H3O+)
D) HNO3/H2SO4
E) SO3/H2SO4
Ans: C
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Chapter 15
Topic: Reagents
ethylbenzene  2- and 4-chloro-1-ethylbenzene
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E) None of these
Ans: B
Topic: Reagents
t-butylbenzene  p-chloro substitution product
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E) HCl, peroxide
Ans: B
Topic: Reagents
toluene  benzyl bromide
A) Br2, FeBr3
B) N-Bromosuccinimide, ROOR, h
C) HBr
D) Br2/CCl4
E) NaBr, H2SO4
Ans: B
Topic: Reagents
33. Which reagent(s) would you use to synthesize 2- and 4-bromo-1-cyclopentylbenzene

from cyclopentylbenzene?
A) N-Bromosuccinimide (NBS), CCl4, light
B) PBr3
C) Br2, FeBr3
D) CH3CH2Br, AlBr3
E) HBr, ROOR
Ans: C
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Chapter 15
Topic: Reagents
34. The compound 4-bromo-1-propylbenzene is best made from benzene by the application
of these reagents in the order shown:
A) (1) Br2,Fe (2) CH3CH2CH2Cl, AlCl3
B) (1) CH3CH2CH2Cl, AlCl3 (2) Br2,Fe
C) 1) CH3CH2CCl , AlCl3 2) Br2, Fe 3) Zn(Hg), HCl
O
D) 1) CH3CH2CCl , AlCl3 2) Zn(Hg), HCl 3) Br2, Fe
O
E) (1) (CH3)2CHCl, AlCl3 (2) Br2,Fe
Ans: D
Topic: Functional Group Tests
35. Which reagent would you use as the basis for a simple chemical test that would
distinguish between toluene and vinylbenzene (C6H5CH=CH2)?
A) NaOH/H2O
B) Br2/CCl4
C) NaBH4
D) HCl/H2O
E) NaI in acetone
Ans: B
Topic: Nomenclature, Functional Group Tests
36. Which reagent or test could you use to distinguish between phenylacetylene and
vinylbenzene?
A) NaOH/H2O
B) Br2/CCl4
C) IR Spectroscopy
D) CrO3/H2SO4
E) Concd. H2SO4
Ans: C
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Chapter 15
Topic: Nomenclature, Synthesis
37. Which of the following would be the best synthesis of 1,4-dimethyl-2-nitrobenzene?

A) HNO3 2 CH3Cl
Benzene product
H2SO4 2 AlCl3
B) HNO3 CH3Cl
Toluene product
H2SO4 AlCl3
C) HNO 3
p-Xylene
H2SO4
D) CH3Cl
m-Nitrotoluene
AlCl3
E) All of these are equally good.
Ans: C
Topic: Synthesis
38. Starting with benzene, the best method for preparing p-nitrobenzoic acid is:
A) HNO3/H2SO4; then CH3Cl/AlCl3; then separation of isomers; then KMnO4/
-
OH/heat, followed by H3O+.
B) CH3Cl/AlCl3; then HNO3/H2SO4; then separation of isomers; then KMnO4/
-
OH/heat, followed by H3O+.
C) CH3Cl/AlCl3; then KMnO4/-OH/heat, followed by H3O+; then HNO3/H2SO4.
D) HNO3/H2SO4; then KMnO4/-OH/heat, followed by H3O+; then CH3Cl/AlCl3.
E) HNO3/H2SO4; then CO2, followed by H3O+.
Ans: B
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Chapter 15
Topic: Synthesis
39. A good synthesis of
O
(CH3)3C CCH3
would be:
A) O
CH3CCl (CH3)3CCl
Benzene
AlCl3 AlCl3
B) O
(CH3)3CCl CH3CCl
Benzene
AlCl3 AlCl3
C) O
CH3CCl (CH3)2C CH2

Benzene
AlCl3 HF
D) More than one of these
E) None of these
Ans: B
Topic: Synthesis
40. Which would be a good synthesis of m-nitrobenzoic acid?

A) HNO3/H2SO4 CH3Cl 1. KMnO4, NaOH, heat
Benzene
heat AlCl3 2. H3O+
B) HNO3/H2SO4 1. KMnO4, NaOH, heat

Toluene
heat 2. H3O+
C) 1. KMnO4, NaOH, heat HNO3/H2SO4
Toluene
2. H3O+ heat
D) More than one of the above
E) None of the above
Ans: C
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Chapter 15
Topic: Synthesis
41. Benzoic acid can be prepared by the oxidation of all of the following compounds except
this one:
A) C6H5CH=CH2
B) C6H5CCH
C) C6H5COCH3
D) C6H5CH2CH2CH3
E) C6H5C(CH3)3
Ans: E
Topic: Synthesis
42. Which of the following reactions would yield isopropylbenzene as the major product?
A) CH3CH CH2
Benzene
H2SO4
B) CH3CHCH3
OH
Benzene
H2SO4
C) CH3CHCH3
Cl
Benzene
AlCl3
D) CH3CH2CH2Cl
Benzene
AlCl3
E) All of these
Ans: E
Topic: Synthesis
43. Which of the following reactions could be used to synthesize tert-butylbenzene?

A) H2SO4
C6H6 + CH2=C(CH3)2
B) H2SO4
C6H6 + (CH3)3COH
C) AlCl3
C6H6 + (CH3)3CCl
D) All of the above
E) None of the above
Ans: D
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Chapter 15
Topic: Synthesis
44. Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?

A) C6H5CH2CH3 + Cl2, Fe 
B) C6H5CH2CH3 + Cl2, 400C 
C) C6H5CH2CH2OH + SOCl2 
D) C6H5CH=CH2 + HCl, peroxide 
E) C6H6 + CH3CH2Cl, AlCl3 
Ans: C
Topic: Synthesis
45. Which of the following reactions would produce isopropylbenzene?

A) Cl
Benzene
AlCl3
B)
Benzene
HF
C) OH
Benzene
H2SO4
D) Br
Benzene
AlCl3
E) All of these
Ans: E
548
Chapter 15
Topic: Synthesis
46. How might the following synthesis be carried out:
CH2CH3
several
Benzene ?
steps Cl
A) CH3CH2Cl Cl2
C6H6 product
AlCl3 FeCl3
B) Cl2 CH3CH2Cl
C6H6 product
FeCl3 AlCl3
C) O
CH3CCl Cl2 Zn(Hg)

C6H6 product
AlCl3 FeCl3 HCl
D) O
CH3CCl Zn(Hg) Cl2

C6H6 product
AlCl3 HCl FeCl3
E) None of these syntheses is satisfactory.
Ans: C
Topic: Synthesis
47. Which is the best sequence of reactions for the preparation of p-bromostyrene from
ethylbenzene?
A) NBS, h Br2 KOH
ethylbenzene product
CCl4 Fe CH3CH2OH
B) Br2 NBS, h KOH
Fe CCl4 CH3CH2OH
C) NBS, h KOH Br2
CCl4 CH3CH2OH Fe
D) ZnO Br2
630 oC Fe
Ans: B
549
Chapter 15
Topic: Synthesis
48. Which is the best sequence of reactions for the following transformation?
O
NO2
A) i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H3O+, heat
B) i) CH3MgBr, Et2O; ii) H3O+, heat; iii) HNO3, H2SO4
C) i) HNO3, H2SO4; ii) NaBH4, H2O; iii) H3O+, heat
D) i) HNO3, H2SO4; ii) NaBH4, H2O; iii) H3O+, heat
Ans: A
Topic: Synthesis
O OH
OCH3
NO2
A) i) HNO3, H2SO4; ii) 2EtMgBr, Et2O; iii) NH4Cl
B) i) 2EtMgBr, Et2O; ii) H3O+; iii) HNO3, H2SO4
C) i) HNO3, H2SO4; ii) NaBH4, H2O; iii) 2EtMgBr, Et2O
D) i) LAH; ii) 2EtLi, Et2O; iii) HNO3, H2SO4, heat
Ans: A
Topic: Synthesis
O
OH
NO2
A) i) SOCl2; ii) C6H6, AlCl3; iii) Zn(Hg),HCl; iv) HNO3, H2SO4
B) i) SOCl2; ii) HNO3, H2SO4; iii) C6H6, AlCl3; iv) H2, Ni
C) i) HNO3, H2SO4; ii) SOCl2; iii) C6H6, AlCl3; iv) Zn(Hg),HCl
D) i) PBr3; ii) HNO3, H2SO4; iii) C6H6, AlCl3; iv) NaBH4, H2O
E) two of these syntheses are satisfactory.
Ans: C
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Chapter 15
Topic: Relative Reactivities
51. Which of the following compounds would be most reactive toward electrophilic
substitution?
OH CH3 Br CHO NO2
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: A
52. Which of the following compounds would be most reactive to ring bromination?
CH3 NO2 CF3 Cl NH2
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: E
53. Which of the following compounds would you expect to be most reactive toward ring
nitration?
A) Benzene
B) Toluene
C) m-Xylene
D) p-Xylene
E) Benzoic acid
Ans: C
551
Chapter 15
54. Which of the following compounds would be least reactive toward electrophilic
substitution?
O
O
NO2 NH
NO2
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B
55. Which of the following compounds would be most reactive toward ring nitration?
O O
O CF3 OH NH
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: D
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Chapter 15
56. Which of the compounds listed below would you expect to give the greatest amount of
meta-product when subjected to ring bromination?
HO O
OH NH2 OCH3 CH3
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B
57. Which of the following compounds would be most reactive toward ring bromination?
O
HO O O O
O NH2 OCH3
O
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: C
553
Chapter 15
58. Which of the compounds listed below would you expect to give the greatest amount of
meta-product when subjected to ring nitration?
O
O NH OCH3 CH3
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B
Topic: Mechanisms and Intermediates
59. Which of the following structures contribute(s) to the resonance hybrid of the
intermediate formed when bromobenzene undergoes para-chlorination?
.. .. .. ..
: Br : : Br + : Br : : Br :
+
+ +
H Cl H Cl H Cl H Cl
I II III IV
A) I
B) II
C) III
D) IV
E) All of the above
Ans: E
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Chapter 15
60. Which of the following contributors to the resonance stabilized hybrid formed when
aniline undergoes para-chlorination would be exceptionally stable?
: NH2 +NH2 : NH2 : NH2
+
+ +
H Cl H Cl H Cl H Cl
I II III IV
A) I
B) II
C) III
D) IV
E) None of these
Ans: B
61. Consider the structures given below. Which of them would be a relatively stable
contributor to the hybrid formed when toluene undergoes para bromination?
CH3 CH3 CH3 CH3 CH3
+
+ + +
H Br Br H Br H Br Br+
I II III IV IV
A) I
B) II
C) III
D) IV
E) V
Ans: C
555
Chapter 15
62. Which of the following structures does not contribute to the resonance hybrid of the
intermediate formed when nitrobenzene undergoes meta-chlorination?
.. .. .. .. .. ..
: O : O: : O : O: : O : O:
N N N
+ H
+H
H
Cl Cl Cl
+
I II III
A) I
B) II
C) III
D) None of these contribute
E) All of these contribute.
Ans: E
63. Which of these is the rate-determining step in the nitration of benzene?

A) Protonation of nitric acid by sulfuric acid
B) Protonation of sulfuric acid by nitric acid
C) Loss of a water molecule by the protonated species to produce the nitronium ion
D) Addition of nitronium to benzene to produce the arenium ion
E) Loss of a proton by arenium ion to form nitrobenzene
Ans: D
Topic: Directing Effects
64. The ortho/para product ratio is expected to be the smallest for the bromination of which
of these?
A) Toluene
B) Isopropylbenzene
C) Butylbenzene
D) sec-Butylbenzene
E) tert-Butylbenzene
Ans: E
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Chapter 15
65. Which of the following is not a meta-directing substituent when present on the benzene
ring?
A) -NHCOCH3
B) -NO2
C) -N(CH3)3+
D) -CN
E) -CO2H
Ans: A
66. Each of the five disubstituted benzenes shown below is nitrated. In which of these cases
does the arrow not indicate the chief position of nitration.
O
Cl COOH Cl NHCOCH3 CCH3
Cl
NO2
OH CH3 CH2CH3
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: C
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Chapter 15
67. Which of the following compounds would yield the greatest amount of meta product
when subjected to ring nitration?
HO O
O
HO O
O HO
HO O
OH
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: A
68. Which of the following is not an ortho-para director in electrophilic aromatic

substitution?
A) -CF3
B) -OCH3
C) -CH3
D) -F
E) -NH2
Ans: A
69. Which of these compounds gives essentially a single product on electrophilic

substitution of a third group?
A) p-chlorotoluene
B) m-ethylanisole
C) 1-bromo-2-chlorobenzene
D) m-xylene
E) 3-hydroxybenzoic acid
Ans: D
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Chapter 15
70. What is a feature found in all ortho-para directing groups?

A) An oxygen atom is directly attached to the aromatic ring.
B) The atom attached to the aromatic ring possesses an unshared pair of electrons.
C) The group has the ability to delocalize the positive charge of the arenium ion.
D) The atom directly attached to the aromatic ring is more electronegative than
carbon.
E) The group contains a multiple bond.
Ans: C
71. Which is the best prediction of the site(s) of substitution when 3-methylphenol is
nitrated?
A) C-2
B) C-4
C) C-5
D) C-6
E) C-4 and C-6
Ans: E
72. (Trifluoromethyl)benzene, C6H5CF3, will

A) nitrate rapidly in the ortho-para positions.
B) nitrate slowly in the ortho-para positions.
C) nitrate rapidly in the meta position.
D) nitrate slowly in the meta position.
E) fail to nitrate under any conditions.
Ans: D
73. What feature is common to all meta-directing groups?

A) The atom directly attached to the ring has a full or well-developed partial positive
charge.
B) The atom directly attached to the ring is doubly bonded to oxygen.
C) One or more halogen atoms are present in the group.
D) One or more oxygen atoms are present in the group.
E) The group is attached to the ring through a carbon atom.
Ans: A
559
Chapter 15
74. Arrange the following compounds in order of decreasing reactivity in electrophilic

substitution:
O
O Br NO2
I II III IV V
A) V > II > I > III > IV
B) II > V > III > I > IV
C) IV > I > III > V > II
D) III > II > I > IV > V
E) IV > V > II > I > III
Ans: B
Topic: Other EAS Considerations
75. Which of these liquids would be unsuitable as an inert solvent for a Friedel-Crafts
reaction?
A) Chlorobenzene
B) Nitrobenzene
C) Acetophenone
D) (Trifluoromethyl)benzene
E) All could be used.
Ans: A
76. Undesired polysubstitution of an aromatic nucleus is most likely to be encountered in

the case of:
A) Friedel-Crafts alkylation
B) Friedel-Crafts acylation
C) Nitration
D) Sulfonation
E) Chlorination
Ans: A
560
Chapter 15
77. This molecule cannot participate as a reactant in a Friedel-Crafts reaction.

A) Benzene
B) Chlorobenzene
C) Nitrobenzene
D) Toluene
E) tert-Butylbenzene
Ans: C
78. Which one of these molecules can be a reactant in a Friedel-Crafts reaction?

A) Aniline
B) Nitrobenzene
C) Chloroethene
D) Bromobenzene
E) p-Bromonitrobenzene
Ans: D
79. This substituent deactivates the benzene ring towards electrophilic substitution but
directs the incoming group chiefly to the ortho and para positions.
A) -OCH2CH3
B) -NO2
C) -F
D) -CF3
E) -NHCOCH3
Ans: C
80. In electrophilic aromatic substitution, the attacking species (the electrophile) necessarily
is a:
A) Neutral species.
B) Positively charged species.
C) Lewis acid.
D) Proton.
E) Carbocation.
Ans: C
561
Chapter 15
81. The electrophilic bromination or chlorination of benzene requires, in addition to the

halogen:
A) Hydroxide ion.
B) A Lewis base.
C) A Lewis acid.
D) Peroxide.
E) Ultraviolet light.
Ans: C
Topic: Non-EAS Reactions
82. What is the Birch reduction product of the following reaction?
Na, NH3(l)
?
EtOH
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: D
83. SN1 solvolysis of C6H5CH=CHCH2Cl in water produces:

A) C6H5CH2C(OH)=CH2
B) C6H5CH=CHCH2OH
C) C6H5CHOHCH=CH2
D) A mixture of B) and C)
E) A mixture of A), B) and C)
Ans: D
562
Chapter 15
84. Which compound is capable of undergoing both SN1 and SN2 reactions in ordinary
nonacidic solvents?
Br Br Br
Br
Br
I II III IV V
A) I
B) II
C) III
D) IV
E) V
Ans: D
85. Which alkyl halide can undergo both SN1 and SN2 reactions in nonacidic solvents?
A) CH3Br
B) CH3CH2CH2Br
C) CH2 CHCHCH3
Br
D) C6H5CH2CH2CH2Br
E) CH3
C6H5CCH2Br
CH3
Ans: C
Topic: Non-EAS Relative Rates and Intermediates
86. The rate of solvolysis in ethanol is least for which of these compounds?
A) C6H5CH2Cl
B) C6H5C(CH3)2
Cl
C) (C6H5)2CHCl
D) C6H5CHCl
CH3
E) (C6H5)3CCl
Ans: A
563
Chapter 15
87. Which of the following structures would not be a contributor to the resonance hybrid of
the benzyl cation?
CH3 CH3 +CH2 CH2 CH3

H
H + +
+
+
I II III IV IV
A) I
B) II
C) III
D) IV
E) V
Ans: A
88. Which of these species is/are proposed as intermediate(s) in the mechanism for the
Birch reduction?
A) Radical
B) Carbanion
C) Radical anion
D) Both A) and B)
E) All of A), B) and C)
Ans: E
564
Chapter 15
89. Which of the following carbocations would be most stable?

A) CH3
C6H5CH2CH2CHCH2
B)
CH2
C6H5CH2CH2CHCH3
C) CH3
C6H5CH2CH2CCH3
D) CH3
C6H5CH2CHCHCH3
E) CH3
C6H5CHCH2CHCH3
Ans: E
90. Which alkyl halide would be most reactive in an SN2 reaction?

A) C6H5CH2CH2CH2Br
B) C6H5CHCH2Br
CH3
C) C6H5CH2CHCH3
Br
D) CH3
C6H5CCH2Br
CH3
E) Br
C6H5CCH3
CH3
Ans: A
565
Chapter 15
91. Which alkyl halide would be most reactive in an SN1 reaction?

A) C6H5CH2CH2CH2Br
B) C6H5CH2CHCH3
Br
C) CH3
C6H5CH2CBr
CH3
D) Br
C6H5CCH3
CH3
E) CH3
C6H5CCH2Br
CH3
Ans: D
SHORT ANSWER QUESTIONS
Topic: General
92. Aromatic hydrocarbons are generally known as ____________.

Ans: arenes
Topic: General Reactivity
93. Benzene is susceptible to electrophilic attack primarily because of its _____________.

Ans: exposed  system
94. Although benzene is susceptible to electrophilic attack, its special stability causes it to
undergo ______________ rather than ____________ reactions.
Ans: substitution; addition
566
Chapter 15
Topic: EAS Mechanism
95. In general, there are three steps to an electrophilic aromatic substitution reaction. These
are:
a) formation of an _____________;
b) reaction with an aromatic ring to form an ___________; and
c) loss of a _________ to reform the aromatic system.
Ans: electrophile; arenium ion; proton
96. Aryl and vinyl halides cannot be used in the Friedel-Crafts alkylation because they do
not __________.
Ans: form carbocations readily
Topic: General EAS Reactivity
97. Substituent groups affect both _____________ and _______________ in electrophilic

aromatic substitution reactions.
Ans: reactivity; orientation
98. Electron-donating groups increase the electron density on the aromatic ring, causing it
to be more reactive than benzene itself towards EAS. These types of groups are called
_____________ groups.
Ans: activating
99. Electron-withdrawing groups decrease the electron density on the aromatic ring, causing
it to be less reactive than benzene itself towards EAS. These types of groups are called
_____________ groups.
Ans: deactivating
100. With the exception of halogens, activating groups are ____________ directors and
deactivating groups are _________ directors.
Ans: ortho/para; meta
567
Chapter 15
101. When two different groups are present on a benzene ring, the ____________ generally
determines the outcome of an EAS reaction.
Ans: more powerful activating group
Topic: EAS/non-EAS Reactivity
102. When toluene reacts with Cl2, the identity of the major product(s) obtained depends on
whether the reaction is carried out in the presence of catalytic amounts of FeCl3, or
without catalyst, at high temp. Explain clearly.
Ans: Reaction with Cl2/FeCl3 results in electrophilic aromatic substitution at the o- and
p- positions, since the methyl group in toluene is an activating, o-,p- director. In
contrast, when the reaction is carried out without catalyst, at high temperature, the
methyl group undergoes free-radical halogenation via the benzyl radical
intermediate.
Cl2 Cl +
FeCl3 Cl
Cl
Cl2
heat
568
Chapter 15
103. When the following substance is treated with Br2/FeBr3, the major product is obtained in
good yield, and only very small amounts of minor products are found. What is this
major product and why are the minor products not formed to any significant degree?
Explain clearly.
O
Br2
HN ?
O
FeBr3
Ans: The major products are produced by brominating Ring B. Ring B is more
electron-rich due to the electron-donation of both the nitrogen and methyl groups
attached versus the two electron-withdrawing carbonyl groups attached to Ring A,
which make it inherently electron-poor. Therefore, bromination mainly occurs on
the more electron-rich benzene ring affording a mixture of the following two
compounds. Due to steric effects, bromination ortho to both the nitrogen and
methyl group would lead to a minor product. Also, because Ring A is electron-
poor, bromination of this ring would also lead to minor products.
Ring Ring
A A
O O
HN Br + HN major products
O O
Ring Br Ring
B B
Topic: Synthetic Strategy
104. Suggest a reasonable synthetic strategy for the synthesis of 3,5-dinitrobenzyl alcohol
from benzaldehyde.
Ans: NO2 NO2
HNO3 (excess) NaBH4
O H2SO4 O H2O OH
O2N O2N
heat
benzaldehyde 3,5-dinitrobenzyl alcohol
105. Suggest a reasonable synthetic strategy for the synthesis of 4-methyl-1-phenyl-1-

pentanol from 4-methylpentanoyl chloride, (CH3)2CHCH2CH2COCl
Ans: O OH
Cl NaBH4
O AlCl3 H2O
4-methylpentanoyl chloride 4-methyl-1-phenyl-1-pentanol
569
Chapter 15
106. Suggest a reasonable synthetic strategy for the synthesis of 6-methyl-3-phenyl-3-

heptanol from 4-methylpentanoyl chloride, (CH3)2CHCH2CH2COCl
Ans: O OH
O
i) C2H5MgBr
Cl
AlCl3 ii) NH4Cl
4-methylpentanoyl chloride 6-methyl-3-phenyl-3-heptanol
Topic: Mechanism, Carbocation Stability
107. Acid-catalyzed hydration of 1-phenyl-1-pentene gives 1-phenyl-1-pentanol almost

exclusively; the other possible hydration product, 1-phenyl-2-pentanol, is not detected at
all. Explain clearly.
Ans: Acid catalyzed hydration of an alkene occurs through a carbocation intermediate.
Although 1-phenyl-1-pentene is symmetrically substituted at the C=C, the relative
stabilities of the two possible carbocation intermediates is significantly different:
although both are secondary carbocations, one is also benzylic and thus stabilized
by resonance. The observation that 1-phenyl-1-pentene gives 1-phenyl-1-
pentanol, almost exclusively, is in accordance with the general trend that acid
catalyzed hydration chiefly tends to afford products formed via the most stable
intermediate carbocation.
H
+
H3O+
+ +
H
H2O
2o, benzylic: 2o, but not benzylic:
stabilized by less stable, not
resonance,formed formed to any
almost exclusively appreciable degree
OH H
+
H OH
chief product not detected
570
Chapter 15
Topic: Spectroscopic Analysis
108. How might 1H NMR spectroscopy be useful in distinguishing between the following
two substances?
O
O
O
O
A B
Ans: The chemical shift of the methyl protons is likely to be markedly different in the
two substances. In A, the signal may be expected at about 3.5-4.0 ppm
(attachment to O), while in B, it is likely to show up at about 2.0 ppm (attachment
to >C=O).
571

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Chapter 15

MULTIPLE CHOICE QUESTIONS

Topic: Reaction Products

1. The major product(s), A, of the following reaction,

CH3CH2 Cl CH3CH2 ClCH2CH2 CH3CH

Topic: Reaction Products

2. What would be the major product(s) of the following reaction?

Topic: Reaction Products

3. The major product(s), C, of the following reaction,

Topic: Reaction Products

4. The major product(s), D, of the following reaction,

Topic: Reaction Products

5. What would be the product of the following reaction sequence?

Topic: Reaction Products

COOH COOH COOH COOH

SO3H SO3H Br SO3H SO3H

Topic: Reaction Products

7. What would be the major product of the following reaction?

Cl CH2CH2CH3 CH2CH2CH3 CHCH2CH3

Topic: Reaction Products

NO2 NO2 NO2 NO2

SO3H SO3H Br SO3H SO3H

Topic: Reaction Products

Topic: Reaction Products

10. What would be the major product(s) of the following reaction?

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

14. The major product(s), D, of the following reaction

Topic: Reaction Products

15. What would be the major product of the following reaction?

Topic: Reaction Products

16. Which would be the major product(s) of the following reaction?

Topic: Reaction Products

17. Which would be the product, X, of the following reaction sequence?

SO2 CO2 CH2

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Nomenclature, Reaction Products

Topic: Nomenclature, Reaction Products

Topic: Reaction Products

NH2 NH2 NH2

33. Which reagent(s) would you use to synthesize 2- and 4-bromo-1-cyclopentylbenzene

Topic: Functional Group Tests

Topic: Nomenclature, Functional Group Tests

Topic: Nomenclature, Synthesis

37. Which of the following would be the best synthesis of 1,4-dimethyl-2-nitrobenzene?

39. A good synthesis of

CH3CCl (CH3)2C CH2

40. Which would be a good synthesis of m-nitrobenzoic acid?

B) HNO3/H2SO4 1. KMnO4, NaOH, heat

43. Which of the following reactions could be used to synthesize tert-butylbenzene?

44. Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?

45. Which of the following reactions would produce isopropylbenzene?

46. How might the following synthesis be carried out:

CH3CCl Cl2 Zn(Hg)

CH3CCl Zn(Hg) Cl2

Topic: Relative Reactivities

Topic: Relative Reactivities

97. Substituent groups affect both _ and ___ in electrophilic