Exam
Name___________________________________
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
1) Draw the structure of N-ethyl-N-methyl-1-hexanamine.
1)
ESSAY. Write your answer in the space provided or on a separate sheet of paper.
2) Draw the structure of 2,3-dimethyl-2-butanamine
3) Draw the structure of piperidine.
4) Draw the structure of 3-pentanamine.
5) Draw the structure of N-propyl-4-methyl-3-octanamine.
6) Provide the systematic name for the compound below.
(CH3 )4N+ Cl7) Provide the name for the compound below.
8) Provide the systematic name for the compound below.
9) Provide the systematic name for the compound below.
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
10) Which of the following is a tertiary amine?
A) N-ethyl-1-propanamine
B) 3-pentanamine
C) cyclohexylamine
D) N,N-dimethylaniline
E) methylamine
10)
1
11) Which of the following is a secondary amine?
A) 3-pentanamine
B) N-ethyl-1-propanamine
C) methylamine
D) N,N-dimethylaniline
E) cyclohexylamine
11)
12) Which of the following amines can be resolved into enantiomers?
A) trimethylamine
B) 3-pentanamine
C) 4-(dimethylamino) pyridine
D) 2-pentanamine
E) dimethylammonium chloride
12)
ESSAY. Write your answer in the space provided or on a separate sheet of paper.
13) Why can't N-methyl-2-propanamine be resolved into isolable enantiomers even though the compound is
chiral?
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
14) Which of the following amines is most soluble in water?
A) (CH3 )3N
B) pyrrolidine
C) ethylamine
D) (CH3 CH2CH2 )2 NH
E) PhNH2
14)
ESSAY. Write your answer in the space provided or on a separate sheet of paper.
15) Which has the higher boiling point, butan-1-ol or 1-butanamine? Explain briefly.
16) Rank the following compounds in order of increasing boiling point (lowest to highest): triethylamine,
cyclohexylamine, di-n-propylamine.
17) How might one distinguish a sample of trimethylamine from a sample of n-propylamine using IR
spectroscopy?
18) How might one distinguish a sample of n-butylamine from a sample of diethylamine using IR spectroscopy?
19) How might the presence of an N-H functionally be indicated using NMR spectroscopy?
20) Since alkyl groups are electron donors, one might conclude that tertiary amines are much more basic than
primary amines. Actually, primary and tertiary amines show similar ranges of basicity. Offer an explanation.
21) Provide the product of the reaction shown below.
2
22) Circle the stronger base in the pair below, and briefly explain your choice.
23) Circle the stronger base in the pair below, and briefly explain your choice.
24) Circle the stronger base in the pair below, and briefly explain your choice.
25) A sample of cyclohexylamine is contaminated with considerable hydrocarbon impurity. How might the sample
be purified using a technique based on solubility differences?
26) Provide the structure of the major organic product in the reaction below.
27) Provide the structure of the major organic product in the reaction below.
28) Why are strongly acidic reagents inappropriate when attempting an electrophilic aromatic substitution with
aniline?
29) Provide the structure of the major organic product in the reaction below.
30) Pyridine does not undergo Friedel-Crafts reactions. Offer an explanation.
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MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
31) When pyrrole undergoes electrophilic aromatic substitution, at which position does substitution
occur?
A) 2-position
B) 4-position
C) 3-position
31)
32) Which of the following chloropyridines readily undergo nucleophilic substitution upon treatment
with NaCN?
A) 4-chloropyridine
B) 3-chloropyridine
C) 2-chloropyridine
D) both A and C
E) both A and B
32)
ESSAY. Write your answer in the space provided or on a separate sheet of paper.
33) Can 2-methyl-2-butanamine be prepared in good yield from the reaction of ammonia with
2-bromo-2-methylbutane? Why or why not?
34) Can 1-hexanamine be prepared in good yield from the reaction of a 1:1 molar ratio of ammonia and
1-bromohexane? Why or why not?
35) Provide the structure of the major organic product in the reaction below.
36) Provide a detailed, stepwise mechanism for the reaction of acetyl chloride with n-propylamine.
37) Provide the structure of the major organic product in the reaction below.
38) Provide the structure of the major organic product in the reaction below.
4
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
39) The Hofmann elimination proceeds via a(n) __________ pathway.
A) SN2
B) E1
C) E2
D) SN1
E) none of the above
39)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
40) Provide the structure of the major organic product in the reaction below.
40)
ESSAY. Write your answer in the space provided or on a separate sheet of paper.
41) Provide the structure of the major organic product in the reaction below.
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
42) Heating a(n) __________ results in a Cope elimination.
A) imine
B) oxime
C) enamine
D) amine oxide
E) quaternary ammonium salt
42)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
43) Provide the structure of the major organic product in the reaction below.
5
43)
ESSAY. Write your answer in the space provided or on a separate sheet of paper.
44) Provide the structure of the major organic product in the reaction below.
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
45) Secondary amines react with the nitrosonium ion to generate:
A) N-nitrosoamines
B) imines
C) oximes
D) anilines
E) diazonium salts
45)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
46) Provide the structure of the major organic product in the reaction below.
ESSAY. Write your answer in the space provided or on a separate sheet of paper.
47) Provide the structure of the major organic product in the reaction below.
48) Provide the structure of the major organic product in the reaction below.
49) Provide the structure of the major organic product in the reaction below.
6
46)
50) Provide the structure of the major organic product in the reaction below.
51) Devise an efficient method for preparing 1-pentanamine from but-1-ene.
52) Devise an efficient method for preparing ethylisopropylamine from ethylamine.
53) Devise an efficient method for preparing cyclohexylamine from cyclohexylmethanol.
54) Devise an efficient method for preparing 3-bromotoluene from toluene.
55) Devise an efficient method for preparing 4-bromobenzonitrile from benzene.
56) Devise an efficient method for preparing p-nitrobenzoic acid from toluene.
57) Devise an efficient method for preparing 1,4-diaminobutane from cyclohexene.
58) Devise an efficient method for preparing 1-pentanamine from 1-chloropentane.
59) Devise an efficient method for preparing m-cresol from m-toluidine.
60) Devise an efficient method for preparing 2-phenylethanamine from 2-phenylethanol.
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
61) Which of the following is not an alkaloid?
A) mescaline
B) cocaine
C) nicotine
D) morphine
E) mesitylene
61)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
62) Provide the structure of N-ethyl-1-butanamine.
62)
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
63) The nitrogen atom of trimethylamine is __________ hybridized which is reflected in the CNC bond
angle of __________.
A) sp3 , 120°
B) sp2 , 108°
C) sp2, 120°
D) sp, 180°
E) sp3 , 108°
63)
ESSAY. Write your answer in the space provided or on a separate sheet of paper.
64) Why can 1,2,2-trimethylaziridine be resolved into enantiomers while N-methyl-1-propanamine cannot?
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65) What common names for 1,4-butanediamine and 1,5-pentanediamine are derived from their characteristic
pungent odors?
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
66) Which of the following amines is most basic?
A) N-ethylaniline
B) pyrrole
C) piperidine
D) aniline
E) N,N-diethylaniline
66)
67) In 1H NMR protons on the α-carbon of amines typically absorb between θ:
A) 1.0 and 2.0 ppm
B) 2.0 and 3.0 ppm
C) 3.0 and 4.0 ppm
D) 6.0 and 7.0 ppm
E) 9.0 and 10.0 ppm
67)
68) In the mass spectrum of dipropylamine, the base peak appears at m/z:
A) 101
B) 86
C) 58
D) 72
E) none of the above
68)
69) When pyridine is treated with a mixture of nitric and sulfuric acids, the major product is:
A) 3-aminopyridine
B) 3-nitropyridine
C) 4-aminopyridine
D) 2-nitropyridine
E) 4-nitropyridine
69)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
70) Devise an efficient method for preparing fluorobenzene from benzene.
70)
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
71) Which of the following compounds is a 2° amine?
A) t-butylamine
B) N-butylpyridinium bromide
C) N-ethylaniline
D) N,N-diethylaniline
E) cyclohexylamine
71)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
72) Provide the structure of 2,4-dimethylpyridine
72)
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73) Provide the IUPAC name for the compound shown below.
73)
74) Arrange the following compounds in order of increasing boiling point:
74)
CH3 NHCH2 CH3, CH3 OCH2 CH3 , (CH3 )3 N, and CH3 CH2 CH2 OH.
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
75) Which of the following amines is the strongest base?
A) pyrrole
B) p-iodoaniline
C) cyclohexylamine
D) imidazole
E) piperidine
75)
76) The α-carbon atom bonded to the nitrogen of an alkylamine usually appears in what chemical shift
(δ) range?
A) 30-50
B) 180-220
C) 80-100
D) 5-20
E) 120-150
76)
77) When pentanal reacts with ethylamine under conditions of acid catalysis, the major organic
product is __________.
A) a ketone
B) a nitrile
C) a hydrazone
D) an oxime
E) an imine
77)
78) When CH3 CH2 CHO reacts with PhNHNH2 under conditions of acid catalysis, the major organic
78)
product is __________.
A) an imine
B) an oxime
C) a nitrile
D) a hydrazone
E) a ketone
79) When a 1° amine reacts with an alkyl sulfonyl chloride, the major organic product is __________.
A) a sulfonamide
B) a nitrile
C) a tosylhydrazone
D) a sulfoxide
E) an oxime
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
80) Provide the formula for nitrous acid.
80)
9
79)
81) Provide the IUPAC name of (CH3 )3CCH2CH2 NHCH2 CH3 .
81)
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
82) The nitrogen's lone pair in pyrrolidine is best described as occupying what type of orbital?
A) sp3
B) s
C) sp2
D) p
E) sp
82)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
83) Arrange the following compounds in order of increasing boiling point: ethyl methyl ether,
1-propanol, N-methylethanamine, and 1-propanamine.
83)
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
84) Sec-Butylamine is the common name of what compound?
A) 2-butanamine
B) 1-butanamine
C) N-methyl-1-propanamine
D) N-ethylethanamine
E) N-methyl-2-propanamine
84)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
85) Arrange the following in order of increasing basicity: aniline, p-nitroaniline, p-toluidine,
and p-methoxyaniline.
85)
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
86) A three-carbon, nitrogen-containing compound exhibits 3 13C NMR peaks (d 11.2, 27.3, and 44.9).
Which of the following compounds best matches this spectral data?
A) CH3 NHCH2 CH3
86)
B) H2NCH2 CH2 CH2OH
C) CH3 CH2C≡N
D) (CH3 )2CHNH2
E) CH3 CH2CH2 NH2
87) Pyridine typically undergoes electrophilic aromatic substitution __________ rapidly than benzene,
and its preferred site of substitution is the __________ - position.
A) more, 3
B) more, 4
C) less, 3
D) more, 2
E) less, 2
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
88) Provide the major organic compound in the following reaction.
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88)
87)
89) Provide the major organic compound in the following reaction.
89)
90) Provide the major organic compound in the following reaction.
90)
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
91) Which of the following compounds containing a tertiary amine?
1)
2)
3)
4)
A) 4
2-methyl-2-propanamine
N-ethylpyrrolidine
N-methylcyclohexylamine
2-(dimethylamino)butanal
B) 3
C) 2 and 4
91)
D) 1
E) 1 and 3
92) Provide the correct IUPAC name for the following amine.
A) 4,N-dimethyl-4-penten-2-amine
C) 2,N-dimethyl-1-penten-4-amine
92)
B) 1,3,N-trimethyl-3-buten-1-amine
D) 4-(methylamino)-2-methyl-1-pentene
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
93) Circle all of the following structures that can be resolved into pure enantiomers.
93)
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
94) Which compound would react most rapidly with sodium methoxide and heat?
A) 2-chloropyridine
B) chlorobenzene
C) 3-chloropyrrole
D) 3-chloropyridine
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94)
95) Which of the following is an intermediate in the mechanism for amide synthesis through acylation
of an amine?
A)
B)
C)
95)
D)
SHORT ANSWER. Write the word or phrase that best completes each statement or answers the question.
96) Complete the short synthesis below by providing the necessary reagents.
96)
MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.
97) Which of the following amines could be formed by reduction of an amide?
1) benzylamine
A) 2 and 3
2) isopropylamine
B) 3 and 4
3) aniline 4) triethylamine
C) 1 and 4
D) 1, 3 and 4
97)
E) 1
98) Physostigmine is used in the treatment of glaucoma. Within this structure, the atom indicated by
__________ is most basic, while atom __________ is least basic.
A) 1 (most basic), 4 (least basic)
B) 2 (most basic), 3 (least basic)
C) 1 (most basic), 3 (least basic)
D) 2 (most basic), 4 (least basic)
E) None of the above
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98)
Answer Key
Testname: W_AMIN
1)
2)
3)
4)
5)
6) tetramethylammonium chloride
7) pyrrole
8) 4-aminocyclohexanone
9) 2-bromo-N-methylaniline
10) D
11) B
12) D
13) Enantiomers interconvert rapidly via nitrogen inversion.
14) C
15) The O-H bond is more polar than the N-H because oxygen is more electronegative than nitrogen. Thus, alcohols form
stronger hydrogen-bonds and have higher boiling points.
16) triethylamine < di-n-propylamine < cyclohexylamine
17) n-Propylamine would show N-H stretches in the IR between 3200 and 3500 cm-1.
18) Primary amines, like n-butylamine, usually show two spikes in the N-H stretching region of the IR between 3200 and
3500 cm -1 while secondary amines usually show only one.
19) Like the O-H group, the N-H group undergoes a rapid H exchange reaction with water. Adding D2 O to the NMR
sample would result in the disappearance of any peaks in the 1H NMR spectrum arising from N-H groups.
20) While tertiary ammonium cations are stabilized to a greater degree by electron donation, they are larger and thus more
poorly solvated.
21)
13
Answer Key
Testname: W_AMIN
22) Pyrrolidine is the stronger base. Protonation of pyrrole results in loss of aromaticity.
23) Diethylamine is the stronger base. The lone pair electrons in pyridine are in an sp2 orbital which is lower in energy
than the sp3 orbital of the lone pair in diethylamine.
24) Cyclohexylamine is the stronger base. The lone pair electrons in aniline are delocalized into the adjacent aromatic π
system.
25) Dissolve sample in ether. Wash with dilute HCl solution to convert the amine to the ammonium hydrochloride which
is water soluble; hydrocarbon remains in ether. Neutralize the aqueous solution with base to reform the amine and
extract with ether.
26)
27)
28) Acidic reagents protonate the amino group transforming it from an activating group to a deactivating group.
29)
30) The presence of the electronegative atom in the ring deactivates it toward reaction with electrophiles. In fact, the
nitrogen lone pair tends to react with electropiles to produce an even further deactivated ring. It should also be noted
that the nitrogen lone pair is in an orbital perpendicular to the ring's π system and could not stabilize the intermediate
carbocation in any event.
31) A
32) D
33) No. SN2 reactions do not proceed with tertiary substrates.
34) No. Problems with multiple alkylation exist.
35)
14
Answer Key
Testname: W_AMIN
36)
37)
38)
39) C
40)
41)
42) D
43)
44)
45) A
15
Answer Key
Testname: W_AMIN
46)
47)
48)
49)
50)
51) 1. HBr, ROOR
2. NaCN
3. LiAlH4
52) CH3 COCH3 , NaBH3CN
53) 1. Na2 Cr2O7 , H2 SO4
2. SOCl2
3. NH3
4. Br2 , NaOH
54) 1. HNO3 , H2 SO4
2. Sn, HCl
3. CH3 COCl
4. Br2 , FeBr3
5. H3 O+
6. H2 SO4 , NaNO2
7. H3 PO2
55) 1. Br2 , FeBr3
2. HNO3 , H2 SO4
3. Sn, HCl
4. H2 SO4 , NaNO2
5. CuCN
16
Answer Key
Testname: W_AMIN
56) 1. HNO3 , H2 SO4
2. Na2 Cr2O7 , H2 SO4
57) 1. KMnO4
2. SOCl2
3. NH3
4. Br2 , NaOH
58) 1. phthalimide anion
2. H2 NNH2, heat
or
1. NaN3
2. LiAlH4 or H2 , Pd
59) 1. NaNO2, HCl
2. H3 O+
60) 1. PCC
2. H2 NOH
3. H2 , Ni or LiAlH4
or
1. SOCl2
2. NaN3
3. LiAlH4 or H2 , Pd
61) E
62) CH3 CH2CH2 CH2 NHCH2 CH3
63) E
64) In 1,2,2-trimethylaziridine the nitrogen atom is contained in a 3-membered ring and cannot readily achieve the sp2
transition state required for nitrogen inversion. Introduction of an sp2 center in a 3-membered ring greatly increases
the angle strain.
65) putrescine and cadaverine
66) C
67) B
68) D
69) B
70) 1. HNO3 , H2 SO4
2. Fe, HCl
3. - OH
4. NaNO2, HCl
5. HBF4
71) C
72)
73) 3,3-dimethyl-1-butanamine
17
Answer Key
Testname: W_AMIN
74) (CH3 )3N < CH3 OCH2 CH3 < CH3 NHCH2 CH3 < CH3 CH2 CH2 OH
75) E
76) A
77) E
78) D
79) A
80) HNO2
81) N-ethyl-3,3-dimethyl-1-butanamine
82) A
83) ethyl methyl ether < N-methylethanamine < 1-propanamine < 1-propanol
84) A
85) p-nitroaniline < aniline < p-toluidine < p-methoxyaniline
86) E
87) C
88)
89)
90)
91) C
92) A
93)
94) A
18
Answer Key
Testname: W_AMIN
95) A
96) 1) NaNO2 / HCl
2) CuCN
3) LiAlH4 or H2 / Pd
97) C
98) A
19