Chapter Twenty

MULTIPLE CHOICE QUESTIONS

Topic: Nomenclature
Section: 20.1
Difficulty Level: Easy

1. Which of the following is a tertiary amine?

A) CH3CH2CH2CH2NH2
B) CH3CH2NHCH2CH(CH3)2
C) (CH3CH2)2NCH2CH(CH3)2
D) (CH3CH2)4N+ OH-
E) (CH3CH2)3CNH2
Ans: C

Topic: Nomenclature
Section: 20.1
Difficulty Level: Medium

2. What type of amine is N-methyl-2-methyl-3-hexanamine?

A) Primary
B) Secondary
C) Tertiary
D) Quaternary
E) None of these
Ans: B

Topic: Nomenclature
Section: 20.1
Difficulty Level: Medium

3. Which is a correct common name for the following substance?

A) Ethylethylisobutylamine
B) Diethylisobutylamine
C) sec-Butyldiethylamine
D) Ethylethyl-sec-butylamine
E) 2-Diethylaminobutane
Ans: C

63
Topic: Nomenclature
Section: 20.1
Difficulty Level: Medium

4. Which is a correct IUPAC name for the following substance?

H
N

A) N-Ethylhexanamine
B) N-Ethylcyclohexanamine
C) N-Cyclohexylethanamine
D) N-Ethylcyclopentanamine
E) N-Ethylaniline
Ans: B

Topic: Nomenclature
Section: 20.1
Difficulty Level: Medium

5. Which is a correct IUPAC name for the following substance?

A) N-Cyclopentyl-N-methylcylopentanamine
B) N-Cyclohexyl-N-methylcylopentanamine
C) N-Cyclopentyl-N-methylcylohexanamine
D) Dicyclopentylmethylamine
E) N-Pentyl-N-methylpentanamine
Ans: A

64
Topic: Nomenclature
Section: 20.1
Difficulty Level: Medium

6. Which of these is properly termed a "quaternary ammonium salt"?

A) (CH3)3CCH2CH2NH3+ Cl
B) (CH3CH2CH(CH3)CH2)2NH2+ Cl
C) (CH3CH2CH2)3NH+ Cl
D) (CH3CH2CH2)4N+ Cl
E) None of these
Ans: D

Topic: Nomenclature
Section: 20.1
Difficulty Level: Hard

7. Which of these is an acceptable alternative name to “(1-methylbutyl)amine”?

A) 2-Aminopentane
B) 2-Pentanamine
C) Isopentylamine
D) sec-Pentylamine
E) Both A) and B)
Ans: E

Topic: Nomenclature
Section: 20.1
Difficulty Level: Hard

8. What type of amine is pyrrolidine?

A) Primary
B) Secondary
C) Tertiary
D) Quaternary
E) None of these
Ans: B

65
Topic: Nomenclature
Section: 20.1
Difficulty Level: Hard

9. What type of amine is N-methylmorpholine?

A) Primary
B) Secondary
C) Tertiary
D) Quaternary
E) None of these
Ans: C

Topic: Nomenclature
Section: 20.1
Difficulty Level: Hard

10. What type of amine is pyrrole?

A) Primary
B) Secondary
C) Tertiary
D) Quaternary
E) None of these
Ans: B

Topic: Nomenclature
Section: 20.1
Difficulty Level: Hard

11. What type of amine is piperidine?

A) Primary
B) Secondary
C) Tertiary
D) Quaternary
E) None of these
Ans: B

66
Topic: Chemical Tests and Separations, Nomenclature
Section: 20.1
Difficulty Level: Hard

12. Which reagent will distinguish between 2-amino-2,3-dimethylpentane and 1-amino-3-

methyl-2-pentene?
A) HONO, 0-5°C
B) C6H5SO2Cl/OH-, then H3O+
C) NaOH
D) HCl
E) Br2/CCl4
Ans: E

Topic: Reactive Intermediates and General Considerations

Section: 20.2
Difficulty Level: Easy

13. Which of these compounds is expected to possess the lowest boiling point?
A) CH3CH2CH2CH2CH2NH2
B) CH3CH2CH2NHCH2CH3
C) (CH3CH2)2NCH3
D) (CH3CH2)2CHOH
E) (CH3)3CCH2NH3+ Cl-
Ans: C

Topic: Chemical Tests and Separations, Nomenclature

Section: 20.3
Difficulty Level: Medium

14. Which reagent could be used to separate a mixture of aniline and toluene?
A) KMnO4 in H2O
B) Dilute NaOH
C) Dilute NaHCO3
D) Ag(NH3)2OH
E) Dilute HCl
Ans: E

67
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

15. Which of the following compounds would be the strongest base?

O
NH2
NH2 NH2

I II III
NH2 NH2

O2 N
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B

Topic: Basicity
Section: 20.3
Difficulty Level: Medium

16. Which of the following compounds would be the weakest base?

O
NH2
NH2 NH2

I II III
NH2 NH2

O2 N
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: A

68
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

17. Which of the following bases has a conjugate acid with the largest pKa?
O
NH2
NH2 NH2

I II III
NH2 NH2

O2 N
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B

Topic: Basicity
Section: 20.3
Difficulty Level: Medium

18. Which of the following bases has a conjugate acid with the smallest pKa?
O
NH2
NH2 NH2

I II III
NH2 NH2

O2 N
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: A

69
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

19. Which of the following compounds would be the strongest base?

N N
NH2
H
I II III
O
OH
N N

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

Topic: Basicity
Section: 20.3
Difficulty Level: Medium

20. Arrange the following amines in order of decreasing basicity (most to least) in aqueous
solution:

NH3 CH3CH2CH2NH2 (CH3CH2CH2)2NH (CH3CH2CH2)3N

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

70
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

21. Arrange the following amines in order of increasing basicity (least to most) in aqueous
solution:

NH3 CH3CH2CH2NH2 (CH3CH2CH2)2NH (CH3CH2CH2)3N

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

Topic: Basicity
Section: 20.3
Difficulty Level: Medium

22. Arrange the following amines in order of decreasing basicity (most to least) in the gas
phase:

NH3 CH3CH2CH2NH2 (CH3CH2CH2)2NH (CH3CH2CH2)3N

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

71
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

23. Arrange the following amines in order of increasing basicity (least to most) in aqueous
solution:
NH2
NH2 NH2 NH2

CF3
I II III IV

A) IV < II < I < III

B) III < II < IV < I
C) III < I < II < IV
D) II < III < I < IV
E) Cannot be determined from information given
Ans: A

72
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

24. Arrange the following amines in order of decreasing basicity (most to least) in aqueous
solution:
NH2
NH2 NH2 NH2

CF3
I II III IV

A) IV > II > I > III

B) III > II > IV > I
C) III > I > II > IV
D) II > III > I > IV
E) Cannot be determined from information given
Ans: C

73
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

25. Which of the following bases has a conjugate acid with the smallest pKa?
NH2
NH2 NH2 NH2

CF3
I II III IV

A) I
B) II
C) III
D) IV
E) Cannot be determined from information given
Ans: D

74
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

26. Arrange the following compounds in order of increasing basicity (least to most) in
aqueous solution:
NH2

H
N
NH2

NO2

I II III IV

A) IV < II < I < III

B) III < II < IV < I
C) II < I < III < IV
D) II < III < I < IV
E) Cannot be determined from information given
Ans: C

75
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

27. Arrange the following compounds in order of increasing basicity (least to most) in
aqueous solution:
NH2

O
NH2

NH2
N

NO2

I II III IV

A) IV < II < I < III

B) III < II < IV < I
C) II < I < III < IV
D) II < III < I < IV
E) Cannot be determined from information given
Ans: C

76
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

G NH3

G pKa

-H 4.58

-+N(CH3)3 2.51

-OCH3 5.29

-CF3 2.57

-Cl 3.81

28. Which of the following aryl amines is the strongest base?

A) Aniline
B) p-Trimethylammonium aniline
C) p-Methoxyaniline
D) p-Trifluoromethylaniline
E) p-Chloroaniline

Ans: C

77
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

G NH3

G pKa

-H 4.58

-+N(CH3)3 2.51

-OCH3 5.29

-CF3 2.57

-Cl 3.81

29. Which of the following aryl amines is the weakest base?

A) Aniline
B) p-Trimethylammonium aniline
C) p-Methoxyaniline
D) p-Trifluoromethylaniline
E) p-Chloroaniline

Ans: B

78
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

30. In aqueous solution, which of the following bases as the conjugate acid possesses the
smallest value for pKa?
A) C6H5NH2
B) NH3
C) (CH3CH2)3N
D) (CH3CH2)2NH
E) CH3CH2CH2NH2
Ans: A

Topic: Basicity
Section: 20.3
Difficulty Level: Medium

31. In aqueous solution, which of the following bases as the conjugate acid possesses the
largest value for pKa?
A) C6H5NH2
B) NH3
C) (CH3CH2)3N
D) (CH3CH2)2NH
E) CH3CH2CH2NH2
Ans: D

79
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

32. Which of these is the strongest acid?

NH3 NH3 NH3

O2N
I II III
NH3
NH3
I
IV V

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

Topic: Basicity
Section: 20.3
Difficulty Level: Medium

33. Which of these is the weakest acid?

NH3 NH3 NH3

O2N
I II III
NH3
NH3
I
IV V

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

80
Topic: Basicity
Section: 20.3
Difficulty Level: Medium

34. Which of these would be predicted to have the smallest pKa?

NH3 NH3 NH3

O2N
I II III
NH3
NH3
I
IV V

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

Topic: Basicity
Section: 20.3
Difficulty Level: Medium

35. Which of these would be predicted to have the largest pKa?

NH3 NH3 NH3

O2N
I II III
NH3
NH3
I
IV V

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

81
Topic: Basicity
Section: 20.3
Difficulty Level: Hard

36. Which would be the weakest base?

A) p-Methylaniline
B) p-Methoxyaniline
C) Hexylamine
D) p-Nitroaniline
E) Dipropylamine
Ans: D

Topic: Basicity
Section: 20.3
Difficulty Level: Hard

37. Which of the following bases has a conjugate acid with the smallest pKa?
A) p-Methylaniline
B) p-Methoxyaniline
C) Hexylamine
D) p-Nitroaniline
E) Dipropylamine
Ans: D

Topic: Reactive Intermediates and General Considerations

Section: 20.3F
Difficulty Level: Easy

38. What is the basis for the successful resolution of racemic C6H5CHOHCO2H through
use of the chiral amine, C6H5CH(NH2)CH3?
A) One enantiomer is more soluble than the other.
B) The racemic mixture is converted into a single isomer in the basic solvent.
C) The diastereomeric salts formed have different solubilities.
D) The diastereomeric salts have different boiling points.
E) The diastereomeric salts have different melting points.
Ans: C

82
Topic: Chemical Tests, Separations and Analysis
Section: 20.3F
Difficulty Level: Hard

39. Which of these could be resolved into separate enantiomers?

A) 4-Methyl-1-pentanamine
B) 4-Methyl-2-pentanamine
C) N-Methyl-1-butanamine
D) N,N-Dimethyl-1-propanamine
E) N-Butyltrimethylammonium bromide
Ans: B

Topic: Reaction Products

Section: 20.4A
Difficulty Level: Medium

40. When an equimolar mixture of ammonia and butyl bromide reacts, which of these
products will form?
A) Butylamine
B) Dibutylamine
C) Tributylamine
D) Tetrabutylammonium bromide
E) All of these
Ans: E

83
Topic: Synthesis
Section: 20.4A
Difficulty Level: Medium

41. Which of the following can be used to prepare 2-aminopentane (pure)?

I. (1mol) 2-bromopentane + (1mol) NH3

LAH
II. (1mol) 2-bromopentane + (1mol) NaN3
Et2O
KOH 2-bromopentane NH2NH2
III. Phthalimide
C2H5OH
A) I
B) II
C) III
D) I and II
E) II and III
Ans: E

Topic: Synthesis
Section: 20.4A
Difficulty Level: Medium

42. Which of the following can be used to prepare allylamine (pure)?

I. (1mol) allyl bromide + (1mol) NH3

LAH
II. (1mol) allyl bromide + (1mol) NaN3 Et2O
KOH allyl bromide NH2NH2
III. Phthalimide C2H5OH
A) I
B) II
C) III
D) I and II
E) II and III
Ans: E

84
Topic: Synthesis
Section: 20.4A
Difficulty Level: Medium

43. Which of the following can be used to prepare benzylamine (pure)?

I. (1mol) benzyl bromide + (1mol) NH3

LAH
II. (1mol) benzyl bromide + (1mol) NaN3 Et2O
KOH benzyl bromide NH2NH2
III. Phthalimide C2H5OH
A) I
B) II
C) III
D) I and II
E) II and III
Ans: E

Topic: Basicity
Section: 20.4A
Difficulty Level: Medium

44. Which of these is the strongest acid?

O O O

NH2 N N
H
I II III
O O

N NH3
H
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: D

85
Topic: Basicity
Section: 20.4A
Difficulty Level: Medium

45. Which of these compounds is soluble in dilute sodium hydroxide solution?

O O O H
S N
NH N

O
I II III
O
N
H N
H
IV V

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

Topic: Synthesis
Section: 20.4B
Difficulty Level: Easy

46. Consider the synthesis below. What is reagent A?

NO2 NH2
A C Br Br
B

A) Br2, FeBr3
B) Fe, HCl; then OH
C) NH2Cl, AlCl3
D) H3PO2
E) LiNH2
Ans: B

86
Topic: Synthesis
Section: 20.4B
Difficulty Level: Easy

47. Consider the synthesis below. What is compound B?

NO2 NH2
A C Br Br
B

NO2 NH2
Br Br Br

I II III
NO2 NH2
Br Br Br

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

Topic: Synthesis
Section: 20.4B
Difficulty Level: Easy

48. Consider the synthesis below. What is reagent C?

NO2 NH2
A C Br Br
B

A) excess Br2, H2O

B) Fe, HCl; then OH-
C) NH2Cl, AlCl3
D) CuBr
E) HNO3, H2SO4, Fe
Ans: A

87
Topic: Synthesis
Section: 20.4B
Difficulty Level: Easy

49. What reagent can effect the following transformation?

NO2 NH2
?

Cl Cl
A) Fe/HCl; then OH-
B) NH2Cl
C) H3PO2
D) CuCN
E) HONO; then NH3
Ans: A

88
Topic: Reaction Products
Section: 20.4C
Difficulty Level: Medium

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

Cl
i) , AlCl3
O ?
ii) (CH3)2NH
iii) LiBH3CN

N O
O N
N

I II III

OH
N

N
IV V

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

89
Topic: Reaction Products
Section: 20.4C
Difficulty Level: Medium

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

Cl
i) , AlCl3
O ?
ii) (CH3)2NH, H2/Pt

N O
O N
N

I II III

OH
N

N
IV V

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

90
Topic: Reaction Products
Section: 20.4C
Difficulty Level: Medium

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

Cl
i) , AlCl3
O ?
ii)
N
H
iii) LiBH3CN

N
O O
N
N

I II III

OH
N
N
IV V

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

91
Topic: Reaction Products
Section: 20.4C
Difficulty Level: Medium

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

Cl
i) , AlCl3
O
?
ii) O NH

iii) LiBH3CN
O
O
N O
O N
N O

I II III

OH
O N
N O
IV V

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

92
Topic: Reaction Products
Section: 20.4C
Difficulty Level: Medium

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

Cl
i) , AlCl3
O
?
ii) NH

iii) LiBH3CN

N O
O N
N

I II III

OH
N
N
IV V

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

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Topic: Synthesis
Section: 20.4C
Difficulty Level: Medium

55. NH2

Which is the best method to prepare ?

A) O
NH3(excess)
H2, Ni
B) Br
NH3

C) CH3NH2
O
H2, Ni
D) NO2
NH2 HONO
+
0-5oC
E) h
+ HNO3
H2, Ni
Ans: A

Topic: Synthesis
Section: 20.4C
Difficulty Level: Medium

56. H
N

Identify the best method(s) to prepare .

A) NH2 CH3I
(1 mol)
(1 mol)
B) (CH3)2NH
O
H2, Ni

C) CH3NH2
O
H2, Ni
D) A) and B)
E) B) and C)
Ans: C

94
Topic: Synthesis
Section: 20.4A and 20.4C
Difficulty Level: Medium

57. Which of the following reactions would yield C6H5CH2NH2?

A) i. NaCN
Br
ii. LiAlH4, ether
iii. H2O
B) NH3
O
H2, Ni
C) Br
i. NaN3
ii. LiAlH4, ether
iii. H2O
D) All of these
E) Answers B) and C) only
Ans: E

95
Topic: Reaction Products
Section: 20.4D
Difficulty Level: Easy

58. What would be the product of the following reaction?

Cl i. NaCN
?
ii. H2, Ni

NH2 N CN
H

I II III

NH2

IV V

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

96
Topic: Reaction Products
Section: 20.4D
Difficulty Level: Easy

59. What would be the product of the following reaction?

Cl i. NaCN ?
ii. LAH

NH2 N CN
H

I II III

NH2

IV V

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

Topic: Reactive Intermediates and General Considerations

Section: 20.4D
Difficulty Level: Easy

60. This type of compound is the only one of these which can be converted by reduction
into a 1, 2 or 3 amine, according to its particular structure:
A) Nitrile
B) Oxime
C) Azide
D) Amide
E) Nitroalkane
Ans: D

97
Topic: Reaction Sequence
Section: 20.4D
Difficulty Level: Medium

61. What is the final product from the following reaction sequence:
O

NH i. LAH
?
ii.H2O

OH
O

NH NH
NH2

III
I II

H2N H2N

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

98
Topic: Reaction Sequence
Section: 20.4D
Difficulty Level: Medium

62. What is the final product from the following reaction sequence:
O

i. LAH
N
?
ii.H2O

OH
O

N N
N
H

III
I II

N N
H H

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

99
Topic: Reaction Sequence
Section: 20.4D
Difficulty Level: Medium

63. What is the final product from the following reaction sequence:
O

i. LAH
N
?
ii.H2O

OH
O

N N
N
H

III
I II

H
N N
H H

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

100
Topic: Reaction Sequence
Section: 20.4D
Difficulty Level: Medium

64. What is the final product from the following reaction sequence:
O

NH i. LAH
?
ii.H2O

OH
O

NH NH
NH2

III
I II

H
H2N H2N

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

101
Topic: Synthesis
Section: 20.4D
Difficulty Level: Medium

66. The overall conversion RBr  RCH2NH2 can be accomplished by

successive application of which of these sets of reagents?
A) Mg, ether; then NH3
B) NaN3; then LiAlH4, ether
C) NaCN; then LiAlH4, ether
D) H2C=O; then NH3
E) H2NOH; then LiAlH4, ether
Ans: C

Topic: Synthesis
Section: 20.4C and 20.4D
Difficulty Level: Medium

66. H
N
Which combination of reactants will not produce ?
A) O
i. LiAlH4, ether
N
H ii. H2O
B)
O
H Zn(Hg), HCl
N
C) + H2N NaBH3CN
O
D) O + H2N NaBH3CN
E) H
N Br2, NaOH
O
Ans: E

102
Topic: Reaction Products
Section: 20.4E
Difficulty Level: Medium

67. What is the final product, C?

O
NH3  H3O+ Br2
O NH4++ C4H5NO3 C4H7NO3 C
excess OH
O

Br O
HO O O  
O2C O2C O N-Br
NH2
NH2 H2N CO2
NH2
O
I II III IV V

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

103
Topic: Synthesis
Section: 20.4E
Difficulty Level: Medium

68. Which of the following might be used to synthesize m-bromoaniline?

A) i. HNO3, H2SO4
ii. Fe, HCl
iii. NaOH, H2O
iv. Br2, H2O
B) Cl
i. Br2, FeBr3
O
ii. HNO3, H2SO4
iii. H2, Pt
C) OH
i. Br2, FeBr3
O
ii. SOCl2
iii. NH3
iv. Br2, NaOH
D) Answers A) and B)
E) Answers B) and C)
Ans: C

Topic: Synthesis
Section: 20.4E
Difficulty Level: Medium

69. What is the final product in the Curtius rearrangement of the acyl azide formed from
butanoyl chloride?
NH2 NH2 N C O

I II III
O O

N N3
H
IV V
A) I
B) II
C) III
D) IV
E) V
Ans A

104
Topic: Reactive Intermediates and General Considerations
Section: 20.4E
Difficulty Level: Medium

70. Which is not an intermediate in the Hofmann degradation reaction?

KOH
RCONH2 RNH2
Br2
A) RN=C=O
B) O

R NHBr
C) O
..
R NBr
..
D) O
R
HO N
H
E) O
Br
R N
Br
Ans: E

Topic: Synthesis
Section: 20.4E
Difficulty Level: Hard

71. Which of the following might be used to synthesize m-bromoaniline?

A) i. HNO3, H2SO4
ii. Fe, HCl
iii. NaOH, H2O
iv. Br2, H2O
B) Cl
i. Br2, FeBr3
O
ii. HNO3, H2SO4
iii. H2, Pt
C) i. Br2, FeBr3
O
ii. I2/OH-
iii. SOCl2
iv. NH3
v. Br2, NaOH
D) Answers A) and B)
E) Answers B) and C)
Ans: C

105
Topic: Synthesis
Section: 20.4E
Difficulty Level: Hard

72. Which of the following might be used to synthesize m-bromoaniline?

A) i. HNO3, H2SO4
ii. Fe, HCl
iii. NaOH, H2O
iv. Br2, H2O
B) Cl
i. Br2, FeBr3
O
ii. HNO3, H2SO4
iii. H2, Pt
C) i. Br2, FeBr3
O
ii. I2/OH-
iii. SOCl2
iv. NaN3
v. heat
D) Answers A) and B)
E) Answers B) and C)
Ans: C

Topic: Reaction Products

Section: 20.4E
Difficulty Level: Hard

73. What final product is expected when toluene is subjected to the following reaction
sequence?
i) KMnO4, NaOH; ii) H3O+; iii) SOCl2; iv) NaN3; v) heat
A) C6H5CONH2
B) C6H5CH2NH2
C) p-CH3C6H4SO2NH2
D) p-CH3C6H4NH2
E) C6H5NH2
Ans: E

106
Topic: Synthesis
Section: 17.8 and 20.4E
Difficulty Level: Medium

74. How could one carry out this synthesis?

O OH
NH2
?
Br Br

A) SOCl2; then NH3; then H3PO2

B) CH3Li, ether; then NH3, H2, Ni
C) SOCl2; then NH3; then Br2, NaOH
D) PCl5; then NH3; then HCl, NaNO2, 0-5°C
E) PCl5; then CH3NH2; then KMnO4, OH-, heat
Ans: C

Topic: Synthesis
Section: 17.8 and 20.4E
Difficulty Level: Medium

75. How could one carry out this synthesis?

O OH
NH2
?
Br Br

A) SOCl2; then NH3; then H3PO2

B) CH3Li, ether; then NH3, H2, Ni
C) SOCl2; then NaN3; then heat
D) PCl5; then NH3; then HCl, NaNO2, 0-5°C
E) PCl5; then CH3NH2; then KMnO4, OH-, heat
Ans: C

107
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

76. What final product is expected when toluene is subjected to the following reaction
sequence?
i) KMnO4, NaOH; ii) H3O+ ( product = C7H6O2); iii) SOCl2;
iv) NH3 (product = C7H7NO); v) Br2, NaOH
A) C6H5CONH2
B) C6H5CH2NH2
C) p-CH3C6H4SO2NH2
D) p-CH3C6H4NH2
E) C6H5NH2
Ans: E

108
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

77. What is the final product of the reaction sequence:

i. SOCl2
OH
?
ii. NH3
iii. NaOH/Br2
O

NH2 Br
NH2

O II III
I

NH2
NH2

O
IV V

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

109
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

78. What is the final product of the reaction sequence:

i. SOCl2
OH
?
Ph ii. NH3
iii. NaOH/Br2
O

NH2 Ph Br
Ph Ph NH2

O II III
I

NH2
Ph Ph NH2

O
IV V

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

110
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

79. What is the final product of the reaction sequence:

i. SOCl2
OH ii. NH3
?
Ph
iii. NaOH/Br2
O

NH2 Ph Br
Ph Ph NH2

O II III
I

NH2
Ph Ph NH2

O
IV V

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

111
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

80. What is the final product of the reaction sequence:

i. SOCl2
OH ii. NH3
?
iii. NaOH/Br2
O

NH2 Br
NH2

O II III
I

NH2
NH2

O
IV V

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

112
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

81. What is the final product of the reaction sequence:

i. SOCl2
(R)-2-ethyl-2-methylpentanoic acid ?
ii. NH3
iii. NaOH/Br2

A) (S)-2-ethyl-2-methylpentanamide
B) (S)-3-methylhexan-3-amine
C) (S)-3-bromo-3-methylhexane
D) (R)-2-ethyl-2-methylpentanamide
E) (R)-3-methylhexan-3-amine
Ans: E

Topic: Reaction Products

Section: 17.8 and 20.4E
Difficulty Level: Hard

82. What is the final product of the reaction sequence:

i. SOCl2
(R)-2-methyl-2-phenylbutanoic acid ?
ii. NH3
iii. NaOH/Br2

A) (S)-2-methyl-2-phenylbutanamide
B) (S)-2-phenylbutan-2-amine
C) (S)-(2-bromobutan-2-yl)benzene
D) (R)-2-methyl-2-phenylbutanamide
E) (R)-2-phenylbutan-2-amine
Ans: E

113
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

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

i) KMnO4, NaOH, heat
ii) H3O+
Br ?
iii) PCl5
iv) NaN3
v) heat
vi) H2O

A) p-bromobenzamide
B) p-bromobenzaldehyde oxime
C) p-bromobenzenesulfonamide
D) p-bromoaniline
E) 4-bromo-3-chlorobenzoic acid
Ans: D

Topic: Reaction Products

Section: 17.8 and 20.4E
Difficulty Level: Hard

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

i) KMnO4, NaOH, heat
ii) H3O+
Br iii) PCl3 ?
iv) NaN3
v) heat
vi) H2O

A) p-bromobenzamide
B) p-bromobenzaldehyde oxime
C) p-bromobenzenesulfonamide
D) p-bromoaniline
E) 4-bromo-3-chlorobenzoic acid
Ans: D

114
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

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

i) KMnO4, NaOH, heat
ii) H3O+
Br iii) SOCl2 ?
iv) NaN3
v) heat
vi) H2O

A) p-bromobenzamide
B) p-bromobenzaldehyde oxime
C) p-bromobenzenesulfonamide
D) p-bromoaniline
E) 4-bromo-3-chlorobenzoic acid
Ans: D

Topic: Reaction Products

Section: 17.8 and 20.4E
Difficulty Level: Hard

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

i) KMnO4, NaOH, heat
ii) H3O+
Br ?
iii) SOCl2
iv) NaN3
v) heat
vi) H2O

A) p-bromobenzamide
B) p-bromobenzaldehyde oxime
C) p-bromobenzenesulfonamide
D) p-bromoaniline
E) 4-bromo-3-chlorobenzoic acid
Ans: D

115
Topic: Reaction Products
Section: 17.8 and 20.4E
Difficulty Level: Hard

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

i) H3O+, heat
ii) SOCl2
Br CN ?
iii) NaN3
iv) heat
v) H2O

A) p-bromobenzamide
B) p-bromobenzaldehyde oxime
C) p-bromobenzenesulfonamide
D) p-bromoaniline
E) 4-bromo-3-chlorobenzoic acid
Ans: D

Topic: Synthesis, Nomenclature

Section: 17.8 and 20.4E
Difficulty Level: Hard

88. Your task is to convert o-xylene into o-diaminobenzene. Which sequence of reagents
constitutes the best method?
A) NaNH2 and heat
B) NBS/CCl4; then NH3; then Br2/OH-
C) KMnO4, OH-, heat; then H3O+; then PCl5; then NH3, then Br2/OH-
D) KMnO4, OH-, heat; then H3O+; then SOCl2; then NH3; then LiAlH4; then Br2/OH-
E) KMnO4, OH-, heat; then H3O+; then NH3 with H2/Ni
Ans: C

116
Topic: Synthesis
Section: 20.4B and 20.4E
Difficulty Level: Medium

89. Which of the following reaction sequences would yield aniline?

A)
i. HNO3, H2SO4
ii. Fe, HCl
iii. NaOH, H2O
B) Cl
i. NH3
O
ii. Br2,OH
C) i. NH3 (excess)
Br
ii. HONO, 0-5oC, ether
iii. H3PO2
D) All of the above
E) Answers A) and B) only
Ans: E

117
Topic: Reaction Products
Section: 20.6A
Difficulty Level: Medium

90. Which product could not be formed during the following reaction?

NH2 HONO
?
0-5oC
OH
OH

I II III

HO OH

IV V

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

Topic: Reactive Intermediates and General Considerations

Section: 20.6B
Difficulty Level: Easy

91. When the process ArNH2  ArY is carried out via an intermediate
diazonium salt, this salt is isolated only in the case in which Y is which of these groups?
A) -F
B) -Cl
C) -Br
D) -I
E) -CN
Ans: A

118
Topic: Reactive Intermediates and General Considerations
Section: 20.6C
Difficulty Level: Easy

92. Which of these alkyl halides cannot be used effectively in a Gabriel amine synthesis?
A) 1-bromopentane
B) 1-bromo-3-methylbutane
C) 2-bromo-3-methylpentane
D) 1-bromo-2,3-dimethylbutane
E) 2-bromo-2,3-dimethylbutane
Ans: E

Topic: Reactive Intermediates and General Considerations

Section: 20.6C
Difficulty Level: Hard

93. The reaction of which of these compounds with nitrous acid results in a stable N-nitroso
compound?
A) C6H5NH2
B) C6H5N(CH3)2
C) CH3CH2CH2CH2CH2NH2
D) C6H5NHCH3
E) CH3CH2CONH2
Ans: D

119
Topic: Synthesis
Section: 20.7
Difficulty Level: Easy

94. Consider the synthesis below. What is reagent “Z”?

NO2 NO2
i. HONO, 0-5oC
ii. "Z"
NH2 Cl
A) CuCl
B) CuCl2
C) NaCl
D) KCl
E) HCl/heat
Ans: A

Topic: Synthesis
Section: 20.7
Difficulty Level: Easy

95. Consider the synthesis below. What is reagent A?

NH2 CN
Br Br i. HCl, NaNO2 Br Br

ii. "A"

A) H3PO2
B) HCN
C) P4O10
D) CuCN
E) CuCl2
Ans: D

120
Topic: Synthesis
Section: 20.7
Difficulty Level: Easy

96. Consider the synthesis below. What is reagent “Y”?

NH2
Br Br Br Br
i. HONO, 0-5oC
ii. "Y"
Cl Cl
A) Br2/FeBr3
B) CuBr
C) CuBr2
D) H3PO2/H2O
E) H3PO4
Ans: D

Topic: Reaction Products

Section: 20.7
Difficulty Level: Medium

97. Identify the compound (Z) formed when aniline is subjected to the following series of
reactions:
i.) NaNO2, H2SO4, dil.H2SO4 0-5oC; ii.) Cu2O, Cu(NO3)2 , H2O

A) C6H5NH2
B) C6H5Cl
C) C6H5OH
D) C6H6
E) None of these
Ans: C

121
Topic: Reaction Products
Section: 20.7
Difficulty Level: Medium

98. Which is the major product of the following reaction?

NH2
i. HONO, 0-5oC
?
ii. , NaOH
OH

OH NO2

OH
I II III

HO
N N
N OH N

IV V
2

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

Topic: Synthesis
Section: 20.7
Difficulty Level: Medium

99. The best synthesis of 3,5-dibromotoluene would be:

A) Toluene, Br2, Fe and heat
B) p-CH3C6H4NH2, Br2, H2O; then HONO, 0-5°C; then H3PO2
C) Toluene, fuming HNO3, H2SO4; then NH3, H2S; then HONO, 0-5°C; then CuBr
D) m-Dibromobenzene, CH3Cl, AlCl3, heat
E) m-Bromotoluene, HNO3, H2SO4; then NH3, H2S; then HONO, 0-5°C; then CuBr
Ans: B

122
Topic: Synthesis
Section: 20.7
Difficulty Level: Medium

100. How would one carry out the following transformation?

?
H2N Cl Cl
A) NaNO2,HCl, 0-5C; then HNO3
B) NaNO2,HCl, 0-5C; then H3PO2
C) NaNO2,HCl, 0-5C; then H2,Ni
D) C6H5SO2Cl, OH-; then HCl
E) NaH, DMSO
Ans: B

123
Topic: Synthesis
Section: 20.7
Difficulty Level: Hard

101. What is the product of the following reaction sequence:

NH2

Br Br
i. HCl, NaNO2
ii. CuCN
?
iii. DIBAL-H
iv. H2O

CN COOH

Br Br Br Br Br Br

I II III

CHO COOH

Br Br Br Br

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

124
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

102. What final product is expected from the following reaction sequence?
i. Fe/HCl
NO2
ii. NaHCO3
?
Cl iii. Br2/H2O
iv. HONO, 0-5oC
v. H3PO2

Br Br Br
OH NO2

Cl Cl Br Cl
I II III
Br Br
PO2H HO2P NO

Cl Br Cl
IV V

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

125
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

103. What final product is expected from the following reaction sequence?
i. Fe/HCl
ii. NaHCO3
NO2 iii. (CH3CO)2O
?
iv. Br2/H2O
Cl
v. OH-/H2O
vi. HONO, 0-5oC
vii. H3PO2

Br Br Br
NO2

Cl Cl Br Cl
I II III
Br Br
PO2H HO2P NO

Cl Br Cl
IV V

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

126
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

104. What compound is likely to be obtained via the following reaction sequence?
NH
i. HONO, 0-5oC
2
Br Br ii. CuCl
?
iii. Fe/HCl
NO2
iv. NaOH, H2O
v. HONO, 0-5oC
vi. H3PO2

Br Br Cl
Br Br Cl Br Br Br Br
Br Br

Cl NO2 PO2H
I II III IV V

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

127
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

105. What compound is likely to be obtained via the following reaction sequence?
NH2 i. HONO, 0-5oC
Br Br
ii. CuBr
iii. Fe/HCl ?
NO2 iv. NaOH, H2O
v. HONO, 0-5oC
vi. H3PO2

Br Br Br
Br Br Br Br Br Br Br
Br Br

Br NO2 PO2H
I II III IV V

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

128
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

106. What compound is likely to be obtained via the following reaction sequence?
NH2 i. HONO, 0-5oC
Br Br
ii. KI
iii. Fe/HCl ?
NO2 iv. NaOH, H2O
v. HONO, 0-5oC
vi. H3PO2

Br Br I
Br Br I Br Br Br Br
Br Br

I NO2 PO2H
I II III IV V

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

129
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

107. What compound is likely to be obtained via the following reaction sequence?
NH2 i. HONO, 0-5oC
Br Br
ii. CuCN
iii. Fe/HCl ?
NO2 iv. NaOH, H2O
v. HONO, 0-5oC
vi. H3PO2

Br Br CN
Br Br CN Br Br Br Br
Br Br

CN NO2 PO2H
I II III IV V

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

130
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

108. What compound is likely to be obtained via the following reaction sequence?
i. HONO, 0-5oC
NH2 ii. CuCN
Br Br
iii. H3O+
iv. Fe/HCl ?
NO2 v. NaOH, H2O
vi. HONO, 0-5oC
vii. H3PO2

Br Br CN
Br Br COOH Br Br Br Br
Br Br

COOH NO2 PO2H

I II III IV V

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

131
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

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

i. Fe/HCl
iv. NaOH, H2O
?
iii. Br2/H2O
NO2
v. HONO, 0-5oC
vi. H3PO2

Cl
Br PO2H

Br Br Br Br
Br Br NO2
OH PO2H NO

I II III IV V

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

132
Topic: Reaction Products
Section: 20.4B and 20.7
Difficulty Level: Medium

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

i. Fe/HCl
iv. NaOH, H2O
?
iii. Cl2/H2O
NO2 v. HONO, 0-5oC
vi. H3PO2

Cl
Cl PO2H

Cl Cl Cl Cl
Cl Cl NO2
OH PO2H NO

I II III IV V

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

Topic: Synthesis
Section: 20.4B, and 20.7
Difficulty Level: Medium

111. The best synthesis of m-dibromobenzene would be:

A) Benzene, Br2, FeBr3, heat
B) Aniline, Br2, H2O; then HONO, 0-5°C; then CuBr
C) Nitrobenzene, HNO3, H2SO4, heat; then Fe/HCl (excess); then 2 HONO, 0-5°C;
then 2 CuBr
D) Bromobenzene, HNO3, H2SO4; then Fe, HCl, C2H5OH, reflux; then HONO, 0-
5°C; then CuBr
E) Answers C) and D)
Ans: C

133
Topic: Synthesis
Section: 20.4B and 20.7
Difficulty Level: Medium

112. Which is the best preparation of benzonitrile, C6H5CN, from benzene?

A) HNO3/H2SO4; then Fe/HCl; then HONO, 0-5°C; then CuCN
B) CH3I, AlCl3; then hot KMnO4; then H3O+; then SOCl2; then NH3; then NaOH +
Cl2
C) CH3I, AlCl3; then Br2, h; then KCN
D) Br2, Fe; then KCN
E) CH3I, AlCl3; then Br2 (2 eq.), h; then hot NaOH; then HCN
Ans: A

Topic: Reaction Products

Section: 20.4B and 20.7
Difficulty Level: Hard

113. What is the final product?

NO2
i. Fe/HCl C7H9N i. Br2(excess) product
ii. OH ii. H2O
i. HONO, 0-5oC
ii. H2O, Cu2O,
Cu(NO3)2

Final Product

A) 2-Bromo-4-methylaniline
B) 2,6-Dibromo-4-methylaniline
C) 2,6-Dibromo-4-methylphenol
D) 2,4-Dibromophenol
E) 3,5-Dibromotoluene
Ans: C

134
Topic: Chemical Tests and Separations
Section: 20.8
Difficulty Level: Medium

114. Which reagent would serve as the basis for a simple chemical test that would distinguish
between the pair of compounds listed below?
NH2
NH2
and

A) AgNO3 in H2O
B) HONO, 0-5°C then -naphthol
C) Dilute NaOH
D) C6H5SO2Cl and OH- in H2O
E) Dilute HCl
Ans: B

135
Topic: Reaction Products
Section: 20.8
Difficulty Level: Medium

115. Which is the major product of the following reaction?

NH2
i. HONO, 0-5oC
?
ii. , NaOH
OH

OH NO2

OH
I II III
OH
N N
N OH N

IV V
2

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

136
Topic: Reaction Products
Section: 20.8
Difficulty Level: Medium

116. Which is the major product of the following reaction?

NH2
i. HONO, 0-5oC
?
ii. , NaOH
N(CH3)2

N(CH3)2 NO2

N(CH3)2
I II III
N(CH3)2
N N
N N(CH3)2 N

IV V
2

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

137
Topic: Reaction Products
Section: 20.8
Difficulty Level: Medium

117. Which is the major product of the following reaction?

NH2
i. HONO, 0-5oC
?
ii. OH , NaOH

OH NO2

HO
I HO II III

N HO
N N
N
IV V
2

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

138
Topic: Synthesis
Section: 20.8
Difficulty Level: Medium

118. What is the principal product when aniline is treated with sodium nitrite and
hydrochloric acid at 0-5C and this mixture is added to p-ethylphenol?
OH OH OH
N
N
N
N

I II III

OH
HO
N
N

IV V

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

139
Topic: Reaction Products
Section: 20.8
Difficulty Level: Hard

119. Which is the major product of the following reaction?

i. HONO, 0-5oC
ii.
NH2 OH
?
H3CO iii. NaOH
iv. CH3I
v. SnCl2

NH2 NO2

H3CO NH2
I II III
NH2
NH2 N
N
H3CO
IV V
2

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

140
Topic: Chemical Tests and Separations
Section: 20.9A
Difficulty Level: Medium

120. Which reagent would serve as the basis for a simple chemical test that would distinguish
between the pair of compounds listed below?
H
NH2 N
and

A) AgNO3 in H2O
B) Dilute NaHCO3
C) Dilute NaOH
D) C6H5SO2Cl/OH-, then H3O+
E) Dilute HCl
Ans: D

Topic: Chemical Tests and Separations

Section: 20.9A
Difficulty Level: Medium

121. Which reagent would serve as the basis for a simple chemical test that would distinguish
between the pair of compounds listed below?
H
NH2 N
and

A) Tollen’s test
B) Jones reagent
C) Hinsberg test
D) Iodoform test
E) None of these
Ans: C

141
Topic: Chemical Tests and Separations
Section: 20.9A
Difficulty Level: Medium

122. Which reagent would serve as the basis for a simple chemical test that would distinguish
between the pair of compounds listed below?
NH2 N
and

A) AgNO3 in H2O
B) Dilute NaHCO3
C) Dilute NaOH
D) C6H5SO2Cl/OH-, then H3O+
E) Dilute HCl
Ans: D

Topic: Chemical Tests and Separations

Section: 20.9A
Difficulty Level: Medium

123. Which reagent would serve as the basis for a simple chemical test that would distinguish
between the pair of compounds listed below?

and

N N
H

A) AgNO3 in H2O
B) Dilute NaHCO3
C) Dilute NaOH
D) C6H5SO2Cl/OH-, then H3O+
E) Dilute HCl
Ans: D

142
Topic: Chemical Tests and Separations
Section: 20.9A
Difficulty Level: Medium

124. Which reagent would serve as the basis for a simple chemical test that would distinguish
between the pair of compounds listed below?

and

N N
H

A) AgNO3 in H2O
B) Dilute NaHCO3
C) Dilute NaOH
D) C6H5SO2Cl/OH-, then H3O+
E) Dilute HCl
Ans: D

Topic: Chemical Tests and Separations

Section: 20.9A
Difficulty Level: Medium

125. Which reagent will distinguish between C6H5NH2 and (C6H5)2NH?

A) HCl (aq)
B) NaOH
C) C6H5SO2Cl/OH-, then H3O+
D) Br2/CCl4
E) KMnO4
Ans: C

143
Topic: Chemical Tests, Separations and Analysis
Section: 20.9A and 20.11
Difficulty Level: Medium

126. Compound W has the molecular formula C11H17N. Treatment of W with

benzenesulfonyl chloride in base gives no reaction. Acidification of the resulting
mixture gives a clear solution. The 1H NMR spectrum of W consists of:

triplet,  1.0
quartet,  2.5
singlet,  3.6 (2H)
multiplet,  7.3 (5H)

The most likely structure for W is:

A) N
H

B) N

C)
N

D) N

E)
N

Ans: B

144
Topic: Reaction Products
Section: 20.12
Difficulty Level: Medium

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

i. CH3I
?
N ii. Ag2O, H2O
iii. heat
OH
N
N N N

I II III IV

A) I
B) II
C) III
D) IV
E) Answers A) and C) only
Ans: A

Topic: Reaction Products

Section: 20.12
Difficulty Level: Medium

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

i. CH3I
ii. Ag2O, H2O ?
N
iii. heat
OH
N
N N N N

I II III IV V

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

145
Topic: Reaction Products
Section: 20.12
Difficulty Level: Medium

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

i. CH3I
ii. Ag2O, H2O ?
N
iii. heat
OH
N
N N N N

I II III IV V

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

Topic: Reaction Products

Section: 20.12
Difficulty Level: Medium

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

i. CH3I
ii. Ag2O, H2O ?
N
iii. heat

N N N N N

I II III IV V

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

146
Topic: Reaction Products
Section: 20.12
Difficulty Level: Medium

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

i. CH3I
ii. Ag2O, H2O ?
N
iii. heat

N N N N N

I II III IV V

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

147
Topic: Synthesis
Section: 20.12
Difficulty Level: Medium

132. What is the chief product of the Hofmann elimination reaction applied to the compound
shown?

N
OH

I II III

IV V

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

148
Topic: Synthesis
Section: 20.12
Difficulty Level: Medium

133. What is the chief product of the Hofmann elimination reaction applied to the compound
shown?

OH

N N N

I II III

N N

IV V

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

149
Topic: Reaction Products
Section: 20.12
Difficulty Level: Hard

134. What is the chief alkene product when butylethylmethylpropylammonium hydroxide is

heated to 150C?
A) CH2=CH2
B) CH3CH=CH2
C) CH3CH2CH=CH2
D) E-CH3CH=CHCH3
E) Z-CH3CH=CHCH3
Ans: A

SHORT ANSWER QUESTIONS

Topic: Nomenclature
Section: 20.1
Difficulty Level: Hard

135. Draw the structure corresponding to the following name:

(4Z,3S)-2,4,7-trimethyl-3-amino-4-octene
Ans:

H2N H

Topic: Nomenclature
Section: 20.1
Difficulty Level: Hard

136. Draw the structure corresponding to the following name:

(3S,6R)-6-(2,4-dinitrophenyl)-3-amino-1-heptyne
Ans: H2N H CH 3

H
NO2

NO2

150
Topic: Stereochemistry
Section: 20.2
Difficulty Level: Easy

137. If the three alkyl groups of a tertiary amine are all different, the amine will be chiral. In
practice, however, it is virtually impossible to separate the two enantiomers, because
they interconvert rapidly through a process called _________________.
Ans: nitrogen inversion or pyramidal inversion

Topic: Amine Structure, Hybridization at Nitrogen

Section: 20.2B
Difficulty Level: Hard

138. Amines are known to rapidly undergo pyramidal inversion at ordinary temperatures,
preventing the resolution of enantiomeric forms when the amine is a chirality center. The
proposed transition state of the inversion process is shown below. Using an orbital diagram,
illustrate the hybridization at nitrogen for this proposed transition state.

R'' R'' R''

N N N
R R
R' R'
R R'

trigonal pyramidal trigonal planar trigonal pyramidal

Ans: In the trigonal pyramidal form, nitrogen is sp3 hybridized. As it proceeds through the
pyramidal inversion process, the structure becomes trigonal planar, with nitrogen now taking
on sp2 hybridization, with the lone pair electrons now residing in an unhybridized p orbital.
The orbital diagram of this hybridized nitrogen is as shown:

sp3 sp2 p

151
Topic: Relative Basicity
Section: 20.3
Difficulty Level: Easy

139. In solution, two factors affect the relative basicity of amines. These factors are:
__________________.
Ans: electron donation by alkyl substituents and stabilization of the alkylaminium ion
by hydrogen bonding with solvent

Topic: Relative Base Strength

Section: 20.3
Difficulty Level: Medium

140. Explain why cyclohexylamine is a stronger base than aniline

Ans: There are two major reasons for the observed difference in basicity between the
two substances:
i) In aniline, the electron pair on N is delocalized over the aromatic ring
through resonance: this has the effect of decreasing the electron
density at the nitrogen atom, relative to cyclohexylamine, in which no
such resonance delocalization can occur, leading to lower base strength
for aniline.
ii) In cyclohexylamine, the N atom is attached to an sp3 carbon, while in
aniline the N atom is attached to an sp2 carbon: an sp2 carbon typically
exerts a stronger electron-withdrawing effect, effectively decreasing
the electron density on the nitrogen atom, resulting in weaker base
strength.

152
Topic: Amine Basicity
Section: 20.3
Difficulty Level: Medium

141. Using resonance theory, explain why guanidine is one of the strongest organic bases.

NH

H2N NH2

guanidine
Ans:
NH NH2

+ OH
+ H 2O
H2N NH2 H2N NH2
The protonated form (conjugate acid) of guanidine is stabilized through three equivalent
resonance structures (shown), making it a very weak acid or the conjugate base a strong
base.
NH2 NH2 NH2

H2N NH2 H2N NH2 H2N NH2

153
Topic: Relative Basicity
Section: 20.3A
Difficulty Level: Easy

142. Arylamines are less basic than alkylamines because of _______________.

Ans: delocalization of the lone pair on nitrogen into the aromatic system

Topic: Amine Basicity and Orbital Hybridization

Section: 3.8A and 20.3
Difficulty Level: Hard

143. List the following compounds in order of increasing basicity (least to most), and
explain your reasoning.

CN NH NH2

I II III

Ans: I < II < III

Reasoning – basicity follows the order of decreasing electronegativity of the nitrogen atom.
Electronegativity of nitrogen is a function of hybridization, with the more s character in the
hybrid orbital, the higher the electronegativity. In I the hybridization of nitrogen is sp,
while in II it is sp2 and in III, sp3.

Topic: Amine Basicity and Orbital Hybridization

Section: 3.8A and 20.3
Difficulty Level: Hard

144. List the following compounds in order of increasing electronegativity (least to most) of
the nitrogen atom, and explain your reasoning.

CN NH NH2

I II III

Ans: III < II < I

Reasoning – Electronegativity of nitrogen is a function of hybridization, with the more s
character in the hybrid orbital, the higher the electronegativity. In I the hybridization of
nitrogen is sp, while in II it is sp2 and in III, sp3.

154
Topic: Relative Basicity
Section: 20.3F
Difficulty Level: Medium

145. Explain how an enantiomerically pure amine can be used to resolve racemic forms of
acidic compounds.
Ans: The amine reacts with the acidic compound to form a pair of diastereomeric salts,
which can be easily separated.

Topic: Multistep Reaction Sequence, Nomenclature

Section: 20.4A
Difficulty Level: Medium

146. Outline the steps involved in the Gabriel synthesis of 3-amino-2-methylpentane.

Ans:
O O O
KOH Br
NH NK N

O O O

NH2NH2
EtOH
reflux

O
NH
+
NH
NH2
O
3-amino-2-methylpentane

155
Topic: Multistep Reaction Sequence, Nomenclature
Section: 20.4A
Difficulty Level: Medium

147. Outline the steps involved in the Gabriel synthesis of allyl amine.
Ans: O O Br O
KOH
NH NK N

O O O

NH2NH2
EtOH
reflux

O
NH
+
NH NH2
O
allyl amine

Topic: Multistep Reaction Sequence, Nomenclature

Section: 20.4A
Difficulty Level: Medium

148. Outline the steps involved in the Gabriel synthesis of allylamine.

Ans: O O Ph Br O
KOH Ph
NH NK N

O O O

NH2NH2
EtOH
reflux

O
NH Ph
+
NH NH2
O
benzylamine

156
Topic: Multistep Reaction Sequence, Nomenclature
Section: 20.4C
Difficulty Level: Medium

149. What final product is likely when acetophenone is subjected to the following reaction
sequence? Give structural details of all significant intermediates.
i) Br2, FeBr3; ii) CH3CH2CH2NH2; ii.) NaBH3CN
Ans:
O O N

Br2 CH3CH2CH2NH2
FeBr3 Br Br

NaBH3CN

NH

Br

Topic: Multistep Reaction Sequence

Section: 20.4C
Difficulty Level: Hard

150. What final product is likely when cyclohexene is subjected to the following reaction
sequence? Give structural details of all significant intermediates.
i) H3O+, H2O; ii) PCC; iii) (CH3)2NH; iv) NaBH3CN
Ans: OH O N
N OH
H3O+ PCC (CH3)2NH NaBH3CN
H 2O

157
Topic: Multistep Reaction Sequence
Section: 20.4C
Difficulty Level: Hard

151. What final product is likely when cyclohexene is subjected to the following reaction
sequence? Give structural details of all significant intermediates.
i) H3O+, H2O; ii) PCC; iii) pyrrolidine; iv) NaBH3CN
Ans: H
N N
OH O N OH
H3O+ PCC NaBH3CN
H2O

Topic: Multistep Reaction Sequence

Section: 20.4C
Difficulty Level: Hard

152. What final product is likely when cyclohexene is subjected to the following reaction
sequence? Give structural details of all significant intermediates.
i) H3O+, H2O; ii) PCC; iii) piperidine; iv) NaBH3CN
Ans:
OH O
H3O+ PCC N N OH NaBH3CN N
H
H 2O

Topic: Multistep Reaction Sequence

Section: 20.4C
Difficulty Level: Hard

153. What final product is likely when cyclohexene is subjected to the following reaction
sequence? Give structural details of all significant intermediates.
i) H3O+, H2O; ii) PCC; iii) morpholine; iv) NaBH3CN
Ans: O O
OH O O
H3O+ PCC N N OH NaBH3CN N
H
H 2O

158
Topic: General, Synthesis of Amines
Section: 20.4C and 20.4D
Difficulty Level: Medium

154. There are two very versatile synthetic methods that can be used to synthesize primary,
secondary, and tertiary amines. These methods are: __________________.
Ans: reductive amination of aldehydes and ketones, and reduction of amides

Topic: Reaction Sequence

Section: 20.4C and 20.4D
Difficulty Level: Medium

155. Propose structures corresponding to each of the molecular formulas given in the
following reaction sequence:

CN H2/Pt
C8H11N C8H15N

O
Ans:

CN CN H2/Pt

O O N
H
C8H11N C8H15N

Topic: Chemical Analysis

Section: 20.6
Difficulty Level: Medium

156. While primary amines react with nitrous acid to generate diazonium salts, secondary
amines react with nitrous acid to produce _____________.
Ans: N-nitrosoamines

159
Topic: Synthetic Strategy and Nomenclature
Section: 20.7
Difficulty Level: Medium

157. Outline the steps involved in the synthesis of 3-chloro-4-fluoroacetophenone from 4-

aminoacetophenone.
Ans: i) Cl2, FeCl3; ii) NaNO2, H3O+, 0-5oC; iii) HBF4; iv) heat

O O O
+
Cl2 NaNO2, H3O
FeCl3 0-5oC
Cl Cl
NH2 NH2 N2+
4-aminoacetophenone i. HBF4
ii. heat
O

Cl
F

160
Topic: Synthetic Strategy and Nomenclature
Section: 20.7
Difficulty Level: Hard

158. Outline the steps involved in the synthesis of 4-bromo-3-nitro-phenol from 4-

bromobenzoic acid
Ans: i) HNO3,H2SO4 ; ii) SOCl2; iii) NH3; iv) Br2, OH-; v) NaNO2, H3O+, 0-5oC
vi) Cu2O, Cu(NO3)2, H2O

O OH O OH O Cl O NH2

HNO3 SOCl2 NH3

H2SO4 NO2 NO2 NO2
Br Br Br Br
4-bromobenzoic acid Br2
NaOH

OH N2+ NH2
Cu2O, Cu(NO3)2 NaNO2, H3O+
NO2 H2O NO2 0-5oC NO2
Br Br Br
4-bromo-3-nitro-phenol

Topic: UV-Vis Absorption

Section: 20.8
Difficulty Level: Medium

159. Azo compounds are usually intensely colored because _________________.

Ans: the N=N linkage brings two aromatic rings into conjugation, giving an extended 
system that generally absorbs in the visible region

161
Topic: Synthetic Strategy and Nomenclature
Section: 20.8
Difficulty Level: Medium

160. What is the principal product when p-toluidine is treated with sodium nitrite and
hydrochloric acid at 0-5C and this mixture is added to o-ethylphenol?
Ans: NaNO2, HCl
NH2 N2+
0-5oC
p-toluidine

OH

OH

N
N

Topic: Product Analysis by NMR

Section: 20.4B and 20.11B
Difficulty Level: Medium

161. You have just completed an experiment involving the reduction of m-nitrobenzoic acid
with Fe/HCl. In order to determine if your reaction has worked as planned, you have
obtained the 1H NMR of your crude product. What will you scrutinize the spectrum for,
in order to help you make this assessment?
Ans: The appearance of 2 new N-H signals, in the range of about 2-6 ppm will be
indicative of successful reduction of the –NO2 group to the –NH2 group. These
signals are characteristically somewhat broad, and should disappear (or decrease
markedly) if the spectrum is rerun with an added drop of D2O to the original
sample prepared for obtaining the 1H NMR. The rest of the signals are likely to
remain more or less similar, with some changes in chemical shift likely (probably
upfield shifts), since the –NO2 group is electron-withdrawing, while the –NH2
group is electron-donating.

162
Topic: Hofmann Elimination
Section: 20.12
Difficulty Level: Easy

162. Eliminations that follow the Hofmann Rule tend to give the ______________ alkene as
the major product.
Ans: least-substituted

Topic: Synthetic Strategy

Section: 20.12
Difficulty Level: Medium

163. What reactant must be used to produce the product shown:

? i. CH3I

ii. Ag2O/H2O
iii. heat
Ans:

163
Topic: Exhaustive Methylation, Hofmann Degradation, Nomenclature
Section: 20.12
Difficulty Level: Hard

164. Before modern spectroscopic methods were developed, structures of many complex
amines were elucidated by examining the products obtained during Hofmann
elimination of their quaternary ammonium hydroxides. The typical procedure involved
the following steps, repeated as necessary, depending on whether the amine was
primary, secondary or tertiary, until the final product was nitrogen-free: i) CH3I (excess);
ii) Ag2O, H2O; iii) heat. What product(s) is (are) likely to be formed if 3,4-
dimethylpiperidine is subjected to the above procedure?
Ans: The reaction sequence would need to be repeated twice to obtain a nitrogen-free
product, since the starting compound is a secondary amine. The final product
expected is 2,3-dimethyl-1,4-pentadiene along with trimethylamine.

CH3I Ag2O heat

N (excess) N I H2O N OH N
H

i. CH3I (excess)
ii. Ag2O, H2O
iii. heat

N +

164
Topic: Reaction Sequence
Section: 20.4C and 20.12
Difficulty Level: Hard

165. In the following sequence fill in the needed reagents.

O NH2

A B, C

Ans:
O NH2

A B, C
NH3/H2/Pt B = excess CH3I
C = Ag2O/H2O

E
m-CPBA

165