Professional Documents
Culture Documents
ch14 PDF
ch14 PDF
HO
Cl
a) m-chorophenol
b) o-chorophenol
c) p-chorophenol
d) o-chorobenzyl alcohol
e) 2-chlorophenyl alcohol
Answer: B
Br
NH 2
a) m-bromoaniline
b) o-bromoaniline
c) p-bromoaniline
d) o-bromobenzyl amine
e) 3-bromophenyl amine
Answer: A
1
3) The correct name for the compound shown below is:
OCH3
O2N
a) o-nitroanisole
b) m-nitroanisole
c) p-nitroanisole
d) p-nitrotoluene
e) 4-nitrophenol
Answer: C
Br
CH 3
a) 3-bromobenzene
b) 4-bromobenzene
c) m-bromobenzene
d) o-bromotoluene
e) Bromomethylbenzene
Answer: D
2
Br Br O
NO2
HO OH HO
NO2 O2N
O O Br
I II III
HO O
Br
Br
HO
O NO2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D
a) Hydroxybenzene
b) Aminobenzene
c) Methylbenzene
d) Ethylbenzene
e) Methoxybenzene
Answer: C
a) Hydroxybenzene
b) Aminobenzene
c) Methylbenzene
d) Ethylbenzene
3
e) Methoxybenzene
Answer: E
a) Hydroxybenzene
b) Aminobenzene
c) Methylbenzene
d) Ethylbenzene
e) Methoxybenzene
Answer: A
a) Hydroxybenzene
b) Aminobenzene
c) Methylbenzene
d) Ethylbenzene
e) Methoxybenzene
Answer: B
a) Hydroxybenzene
b) Aminobenzene
c) Dimethylbenzene
d) Ethylbenzene
e) Methoxybenzene
4
Answer: C
a) Hydroxybenzene
b) Aminobenzene
c) Ethylbenzene
d) Isopropylbenzene
e) Isobutylbenzene
Answer: D
12) The correct name for the compound shown below is:
Br
Br
NH2
a) 3,4-Dibromoaniline
b) 2,4-Dibromoaniline
c) 2,5-Dibromoaniline
d) 3,6-Dibromoaniline
e) 2,6-Dibromoaniline
Answer: C
5
Br Br
NH2
Br NO2
NO2
NH2 NO2 H2N
I II III
OCH3 Br
Br H3CO
NO2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
Br Br
NH2
Br NO2
NO2
NH2 NO2 H2N
I II III
OCH3 Br
Br H3CO
NO2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
6
Answer: B
Br Br
NH2
Br NO2
NO2
NH2 NO2 H2N
I II III
OCH3 Br
Br H3CO
NO2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
7
Cl
Cl SO 3HCl
SO3 H
Cl SO 3H HOOC
I II III
HO3 S HOOC
Cl Cl
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D
Br Br
NH2
Br NO2
NO2
NH2 NO2 H2N
I II III
OCH3 Br
Br H3CO
NO2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
8
Answer: A
I II III
OH OH
Cl Cl
NH2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D
O2 N O 2N O 2N
I II III
O O
O 2N O 2N
H
Br
Br
IV V
9
a) I
b) II
c) III
d) IV
e) V
Answer: C
I II III
OH OH
Cl Cl
NH2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: B
10
Cl Cl
OH O
Cl O
NH2 NO2 H2N
I II III
OH OH
Cl Cl
NH2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
I II III
OCH3 OCH3
Br Br
NH2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D
Br Br
OCH3 Br
H3CO O
NH2 NO2 H2N
I II III
OCH3 OCH3
Br Br
NH2 NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: B
O2 N O 2N O 2N
I II III
O O
O 2N O 2N
H
Cl
Cl
IV V
a) I
12
b) II
c) III
d) IV
e) V
Answer: B
25) In theory, a single molecule of this compound will rotate plane-polarized light.
a) Butylbenzene
b) Isobutylbenzene
c) sec-Butylbenzene
d) tert-Butylbenzene
e) None of these choices.
Answer: C
a) o-Dichlorobenzene
b) m-Dichlorobenzene
c) p-Dichlorobenzene
d) None of these choices.
e) All of these choices.
Answer: B
a) o-Dibromobenzene
b) m-Dibromobenzene
13
c) p-Dibromobenzene
d) More than one of these choices.
e) None of these choices.
Answer: C
28) If thiophene is an aromatic molecule and reacts similarly to benzene, how many (neutral)
monobromothiophenes could be obtained in the following reaction?
S
Br2
FeBr3
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: B
I II III
IV V
a) I
b) II
c) III
d) IV
e) V
14
Answer: A
a) 7
b) 8
c) 9
d) 10
e) 12
Answer: D
a) 2
b) 3
c) 4
d) 5
e) 6
Answer: A
CH3
a) sec-Hexylbenzene
b) 2-Phenylhexane
c) (R)-2-Phenylhexane
15
d) (S)-2-Phenylhexane
e) Butylmethylphenylmethane
Answer: D
a) sec-Hexylbenzene
b) 2-Phenylhexane
c) (R)-2-Phenylhexane
d) (S)-2-Phenylhexane
e) Butylmethylphenylmethane
Answer: C
a) o-Dibromobenzene
b) m-Dibromobenzene
c) p-Dibromobenzene
d) All of these choices.
e) None of these choices.
Answer: B
Answer: C
a) 8
b) 7
c) 6
d) 5
e) 4
Answer: C
a) 8
b) 7
c) 6
d) 5
e) 4
Answer: C
17
a) 8
b) 7
c) 6
d) 5
e) 4
Answer: C
39) Which is the only one of these reagents which will react with benzene under the specified
conditions?
Answer: A
40) Which reagent(s) would serve as the basis for a simple chemical test that would distinguish
between benzene and 1-hexene?
a) NaOH in H2O
b) Br2 in CCl4
c) AgNO3 in C2H5OH
d) NaHSO3 in H2O
e) None of these choices.
Answer: B
41) Which reagent(s) would serve as the basis for a simple chemical test that would distinguish
18
between benzene and cyclohexene?
a) NaOH in H2O
b) Br2 in CCl4
c) AgNO3 in C2H5OH
d) NaHSO3 in H2O
e) None of these choices.
Answer: B
42) Which reagent(s) would serve as the basis for a simple chemical test that would distinguish
between ethylbenzene and vinylcyclohexane?
a) H2CrO4
b) LAH
c) NaBH4, H2O
d) KMnO4, OH−, H2O
e) Two of these choices.
Answer: D
43) Which reagent(s) would serve as the basis for a simple chemical test that would distinguish
between ethylbenzene and vinylcyclohexane?
a) H2CrO4
b) LAH
c) NaBH4, H2O
d) O3/Zn, H+
e) Two of these choices.
Answer: D
19
44) Which reagent(s) would serve as the basis for a simple chemical test that would distinguish
between naphthalene and 2,4,6-decatriene?
a) NaOH in H2O
b) KMnO4, OH−, H2O
c) NaBH4, H2O
d) H2CrO4
e) None of these choices.
Answer: B
a) It is easily reduced.
b) Hydrogen is a small molecule.
c) 1,3-Cyclohexadiene has no resonance energy.
d) It would gain considerable stability by becoming benzene.
e) It would not undergo dehydrogenation.
Answer: D
46) Recalling that benzene has a resonance energy of 152 kJ mol-1 and naphthalene has a
resonance energy of 255 kJ mol-1, predict the positions which would be occupied by bromine
when phenanthrene (below) undergoes addition of Br2.
3 4 5 6
2 7
1 8
10 9
a) 1, 2
b) 1, 4
c) 3, 4
d) 7, 8
20
e) 9, 10
Answer: E
Answer: E
48) Cyclopentadiene is unusually acidic for a hydrocarbon. An explanation for this is the
following statement.
Answer: C
49) Consider the molecular orbital model of benzene. In the ground state how many molecular
orbitals are filled with electrons?
a) 1
b) 2
c) 3
21
d) 4
e) 5
Answer: C
50) In the molecular orbital model of benzene, how many pi-electrons are delocalized about the
ring?
a) 2
b) 3
c) 4
d) 5
e) 6
Answer: E
51) In the molecular orbital model of benzene, how many pi-electrons are in bonding molecular
orbitals?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: A
22
I CH2 CH CH CH2 + H2
II CH2 CH CH2 + H2
IV CH2 CH CH2 + H2
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: B
I + H2
II + H2
III + H2
IV + H2
23
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: B
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: D
24
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: A
56) Application of the polygon-and-circle technique reveals that single electrons occupy each of
the two nonbonding orbitals in the molecular orbital diagram of:
a) Cyclobutadiene
b) Benzene
c) Cyclopropenyl cation
d) Cyclopentadienyl anion
e) Cycloheptatrienyl cation
Answer: A
57) In the molecular orbital model of benzene, the six p-orbitals combine to form how many
25
molecular orbitals?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: A
58) In the molecular orbital model of benzene, how many π-bonding molecular orbitals are
there?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: D
59) In the molecular orbital model of benzene, how many π-antibonding molecular orbitals are
there?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: D
26
60) In the molecular orbital model of benzene, how many pairs of degenerate π-molecular
orbitals are there?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: E
61) In the molecular orbital model of benzene, how many pairs of degenerate π-bonding
molecular orbitals are there?
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: A
62) In the molecular orbital model of benzene, how many pairs of degenerate π-antibonding
molecular orbitals are there?
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: A
27
Difficulty Level: Medium
63) In the molecular orbital model of benzene, how many non-bonding molecular orbitals are
there?
a) 1
b) 2
c) 3
d) 4
e) 0
Answer: E
64) In the molecular orbital model of the cyclopentadienyl cation, how many π-bonding
molecular orbitals are there?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: D
65) In the molecular orbital model of the cyclopentadienyl cation, how many π-antibonding
molecular orbitals are there?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: E
28
Topic: Molecular Orbital Theory
Section: 14.6 and 14.7
Difficulty Level: Medium
66) In the molecular orbital model of the cyclopentadienyl cation, how many pairs of degenerate
π-molecular orbitals are there?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: E
67) In the molecular orbital model of the cyclopentadienyl cation, how many pairs of degenerate
π-bonding molecular orbitals are there?
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: A
68) In the molecular orbital model of the cyclopentadienyl cation, how many pairs of degenerate
π-antibonding molecular orbitals are there?
a) 1
b) 2
c) 3
d) 4
e) 5
29
Answer: A
69) In the molecular orbital model of the cyclopentadienyl cation, how many non-bonding
molecular orbitals are there?
a) 1
b) 2
c) 3
d) 4
e) 0
Answer: E
70) In the molecular orbital model of cyclobutadiene, how many π-bonding molecular orbitals
are there?
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: A
71) In the molecular orbital model of cyclobutadiene, how many π-antibonding molecular
orbitals are there?
a) 5
b) 4
c) 3
d) 2
30
e) 1
Answer: E
72) In the molecular orbital model of cyclobutadiene, how many pairs of degenerate π-molecular
orbitals are there?
a) 0
b) 1
c) 2
d) 3
e) 4
Answer: A
73) In the molecular orbital model of the cyclobutadiene, how many pairs of degenerate π-
bonding molecular orbitals are there?
a) 1
b) 2
c) 3
d) 4
e) 0
Answer: E
74) In the molecular orbital model of cyclobutadiene, how many pairs of degenerate π-
antibonding molecular orbitals are there?
a) 1
b) 2
31
c) 3
d) 4
e) 0
Answer: E
75) In the molecular orbital model of cyclobutadiene, how many non-bonding molecular orbitals
are there?
a) 1
b) 2
c) 3
d) 4
e) 0
Answer: B
76) Consider the molecular orbital model of cyclopentadienyl anion. In the ground state how
many molecular orbitals are filled with electrons?
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: C
77) In the molecular orbital model of cyclopentadienyl anion, how many pi-electrons are
delocalized about the ring?
32
a) 2
b) 3
c) 4
d) 5
e) 6
Answer: E
78) In the molecular orbital model of cyclopentadienyl anion, how many pi-electrons are in
bonding molecular orbitals?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: A
79) In the molecular orbital model of cycloheptadienyl cation, how many pi-electrons are in
bonding molecular orbitals?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: A
80) In the molecular orbital model of cycloheptadienyl cation, how many pi-electrons are
33
delocalized about the ring?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: A
81) In the molecular orbital model of 1,3-cyclobutadiene, how many electrons are in non-
bonding molecular orbitals?
a) 6
b) 5
c) 4
d) 3
e) 2
Answer: E
82) In the molecular orbital model of which of the following substance(s) are non-bonding
orbitals found?
a) 1,3-Cyclobutadiene
b) Cyclopentadienyl anion
c) 1,3,5,7-Cyclooctatetraene
d) Two of these choices.
e) All of these choices.
Answer: D
34
83) Which of the following is NOT true of benzene?
a) Benzene tends to undergo substitution rather than addition reactions, even though it has a high
index of hydrogen deficiency.
b) All of the hydrogen atoms of benzene are equivalent.
c) The carbon-carbon bonds of benzene are alternately short and long around the ring.
d) Only one o-dichlorobenzene has ever been found.
e) Benzene is more stable than the hypothetical compound 1,3,5-cyclohexatriene.
Answer: C
Answer: B
a) of equal length and are shorter than the double bond of ethene.
b) of equal length and are intermediate between a double bond and a single bond.
c) of unequal length and are alternately short and long around the ring.
d) due only to p-orbital overlap.
e) of equal length and intermediate between the carbon-carbon bond lengths in ethene and
ethyne.
Answer: B
35
86) We now know that the two Kekule structures for benzene are related in the following way:
Answer: D
87) In which of the following compounds would the shortest carbon-carbon bond(s) be found?
a) Toluene
b) 2-Ethylcyclopentene
c) 4-Methyl-1,3-cyclohexadiene
d) 3-Methyl-1-hexyne
e) 3-Methyl-1,3-hexadiene
Answer: D
88) In which of the following compounds would the longest carbon-carbon bond(s) be found?
a) 2-Bromobenzaldehyde
b) Vinylbenzene
c) 1,3,5-Heptatriene
d) 2,4,6-Octatriene
e) 2-Ethylbenzoic acid
Answer: D
36
89) Which of the following statements regarding the cyclopentadienyl radical is correct?
a) It is aromatic.
b) It is not aromatic.
c) It obeys Huckel's rule.
d) It undergoes reactions characteristic of benzene.
e) It has a closed shell of 6 pi-electrons.
Answer: B
90) Which of the following statements regarding the cycloheptatrienyl radical is correct?
a) It is aromatic.
b) It is not aromatic.
c) It obeys Hückel's rule.
d) It undergoes reactions characteristic of benzene.
e) It has a closed shell of 6 pi-electrons.
Answer: B
91) Which of the following statements regarding the cyclopentadienyl cation is correct?
a) It is aromatic.
b) It is not aromatic.
c) It obeys Hückel’s rule.
d) It undergoes reactions characteristic of benzene.
e) It has a closed shell of 6 pi-electrons.
Answer: B
37
92) Which of the following statements regarding the cyclopropenyl anion is correct?
a) It is aromatic.
b) It is not aromatic.
c) It obeys Hückel’s rule.
d) It undergoes reactions characteristic of benzene.
e) It has a closed shell of 6 pi-electrons.
Answer: B
93) Which of the following statements regarding the cyclopropenyl radical is correct?
a) It is aromatic.
b) It is not aromatic.
c) It obeys Hückel’s rule.
d) It undergoes reactions characteristic of benzene.
e) It has a closed shell of 6 pi-electrons.
Answer: B
94) Which of the following statements regarding the cycloheptatrienyl anion is correct?
a) It is aromatic.
b) It is not aromatic.
c) It obeys Hückel’s rule.
d) It undergoes reactions characteristic of benzene.
e) It has a closed shell of 6 pi-electrons.
Answer: B
38
95) Of Hückel’s requirements for aromatic character, only this one is waived in the case of
certain compounds considered to be aromatic.
Answer: B
H
H
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E
H
H 2+
I II III IV V
a) I
b) II
39
c) III
d) IV
e) V
Answer: E
H H
I II III IV
a) I
b) II
c) III
d) IV
e) None of these choices.
Answer: B
99) Which of the following would you expect to show aromatic character?
a) I
b) II
c) III
d) IV
e) None of these choices.
40
Answer: B
I II III IV
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: A
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: A
41
102) Which of the following would you expect to be aromatic?
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: A
a) I
b) II
c) III
d) IV
e) V
Answer: B
42
104) Which of the following would you expect to be aromatic?
H H
I II III IV
a) I
b) II
c) III
d) IV
e) None of these choices.
Answer: C
a) I
b) II
c) III
d) IV
e) None of these choices.
Answer: C
106) On the basis of molecular orbital theory and Hückel’s rule, which molecules and/or ions
should be aromatic?
43
H H H
H
I II III IV V
N
H H H H
VI VII VIII IX
a) I and V
b) III and VIII
c) IV, VII and IX
d) IV, VI, VII and IX
e) All of the structures, I-IX
Answer: D
107) On the basis of molecular orbital theory and Hückel’s rule, which molecules and/or ions
should be antiaromatic?
H H H
H
I II III IV V
N
H H H H
VI VII VIII IX
a) I and V
b) I, II and V
c) III and VIII
44
d) IV, VII and IX
e) IV, VI, VII and IX
Answer: B
108) On the basis of molecular orbital theory and Hückel’s rule, which molecules and/or ions
should be non-aromatic?
H H H
H
I II III IV V
N
H H H H
VI VII VIII IX
a) I and V
b) I and II
c) III and VIII
d) IV, VII and IX
e) IV, VI, VII and IX
Answer: C
109) On the basis of molecular orbital theory and Hückel’s rule, which of these compounds
should be aromatic?
45
H H
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E
110) On the basis of molecular orbital theory and Hückel’s rule, which of these compounds
should be aromatic?
a) I
b) II
c) III
d) IV
e) V
Answer: E
111) On the basis of molecular orbital theory and Hückel’s rule, which of these compounds
should be aromatic?
46
a) I
b) II
c) III
d) IV
e) V
Answer: E
N O B
N S
CH3 CH3
H O
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: A
47
a) I
b) II
c) III
d) IV
e) V
Answer: A
a) I
b) II
c) III
d) IV
e) V
Answer: A
48
a) I
b) II
c) III
d) IV
e) V
Answer: A
a) I
b) II
c) III
d) IV
e) V
Answer: D
49
117) Of the following C-10 compounds, which is expected to possess the greatest resonance
(delocalization) energy?
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
119) Which of these would you expect to have significant resonance stabilization energy?
50
N
H N
I II III
a) I
b) II
c) III
d) All of these choices.
e) None of these choices.
Answer: D
120) Which of these would you expect to have significant resonance stabilization energy?
I II III
a) I
b) II
c) III
d) All of these choices.
e) None of these choices.
Answer: D
121) Which of these would you expect to have significant resonance stabilization energy?
51
a) I
b) II
c) III
d) All of these choices.
e) None of these choices.
Answer: D
122) Which of these would you expect to have significant resonance stabilization energy?
I II III
a) I
b) II
c) III
d) All of these choices.
e) None of these choices.
Answer: D
123) Which of these would you expect to have significant resonance stabilization energy?
52
CH
I II III
a) I
b) II
c) III
d) All of these choices.
e) None of these choices.
Answer: D
S N O B
N
H R
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E
53
a) I
b) II
c) III
d) IV
e) V
Answer: E
S N O
N
H
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E
54
O O
N O N O S
H H
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: B
128) In which case is the indicated unshared pair of electrons NOT a contributor to the π
aromatic system?
N O
N
H H
I II III IV
a) I
b) II
c) III
d) IV
e) None of these choices.
Answer: B
129) In which case is the indicated unshared pair of electrons NOT a contributor to the π
aromatic system?
55
S
O
N
H
I II III IV
a) I
b) II
c) III
d) IV
e) None of these choices.
Answer: B
O O
N O N O S
H H
IV V
I II III
a) I
b) II
c) III
d) IV
e) V
Answer: B
56
O
O O
N N O S
H H
IV V
I II III
a) I
b) II
c) III
d) IV
e) V
Answer: B
O O
N S N O S
H H
IV V
I II III
a) I
b) II
c) III
d) IV
e) V
Answer: B
57
O O
N N O N O S
H H H
IV V
I II III
a) I
b) II
c) III
d) IV
e) V
Answer: B
O O
N
N S N O N O
H H H
III IV V
I II
a) I
b) II
c) III
d) IV
e) V
Answer: E
58
O
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
59
O
I II IV V
III
a) I
b) II
c) III
d) IV
e) V
Answer: C
a) [6]-Annulene
b) [14]-Annulene
c) [16]-Annulene
d) [18]-Annulene
e) [22]-Annulene
Answer: C
60
O
N O B
N S
CH3
CH3 H O
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: A
140) On the basis of molecular orbital theory and Hückel’s rule, which of these compounds
should be aromatic?
H H
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E
61
141) How many equivalent resonance structures can be written for the cyclopentadienyl anion?
a) 3
b) 4
c) 5
d) 6
e) 7
Answer: C
142) How many equivalent resonance structures can be written for the cycloheptatrienyl cation?
a) 3
b) 4
c) 5
d) 6
e) 7
Answer: E
143) How many equivalent resonance structures can be written for the cyclopropenyl cation?
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: C
144) How many equivalent resonance structures can be written for the cyclobutadienyl dication?
62
a) 1
b) 2
c) 3
d) 4
e) No equivalent resonance forms can be drawn.
Answer: D
145) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: D
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
146) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 1
b) 2
c) 3
d) 4
63
e) 5
Answer: C
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
147) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 1
b) 2
c) 3
d) 4
e) 5
Answer: E
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
148) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 2
b) 3
c) 4
d) 5
e) 6
Answer: E
Topic: Spectroscopy
64
Section: 14.11
Difficulty Level: Medium
149) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
CHO
Cl
a) 2
b) 3
c) 4
d) 5
e) 6
Answer: D
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
150) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 3
b) 4
c) 5
d) 6
e) 7
Answer: E
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
65
151) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 2
b) 3
c) 4
d) 5
e) 6
Answer: B
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
152) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 4
b) 5
c) 6
d) 7
e) 8
Answer: E
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
153) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
66
a) 4
b) 5
c) 6
d) 7
e) 8
Answer: A
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
154) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 4
b) 5
c) 6
d) 7
e) 8
Answer: E
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
155) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 4
67
b) 5
c) 6
d) 7
e) 8
Answer: B
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
156) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 5
b) 6
c) 7
d) 8
e) 9
Answer: E
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
157) How many resonances would be expected in the broad-band decoupled C-13 spectra of:
a) 4
b) 5
c) 6
d) 7
e) 8
68
Answer: E
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
158) Which of these compounds absorbs at the longest wavelength in the UV-visible region?
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: B
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
159) A compound has the formula C8H9Br. Its 1H NMR spectrum consists of:
doublet, δ 2.0
quartet, δ 5.15
multiplet, δ 7.35
The IR spectrum shows two peaks in the 680-840 cm-1 region; one is between 690 and 710 cm-1
and the other is between 730 and 770 cm-1. Which is a possible structure for the compound?
Br Br
Br
I II III
Br
Br
IV V
a) I
b) II
69
c) III
d) IV
e) V
Answer: D
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
160) Which of the following substances, formula C8H9Br, might exhibit the following 1H NMR
spectrum?
triplet, δ 2.8
triplet, δ 4.65
multiplet, δ 7.2
Br Br
Br
I II III
Br
Br
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
161) Which of the following substances, formula C8H9Br, might exhibit the following 1H NMR
spectrum?
triplet, δ 1.2
quartet, δ 2.45
multiplet, δ 7.4
70
Br Br
Br
I II III
Br
Br
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
162) Which of the following substances, formula C8H9Br, might exhibit the following 1H NMR
spectrum?
singlet, δ 2.45
singlet, δ 2.5
multiplet, δ 7.35
Br Br
Br
I II III
Br
Br
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E
71
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
163) Which of the following substances, C8H9Cl, would exhibit five signals in its 13C NMR
spectrum?
Cl
Cl Cl
I II III
Cl
Cl
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
164) Which of the following substances, C9H10O, would exhibit seven signals in its 13C NMR
spectrum?
O
O
O
I II III
HO
O
IV V
a) I
b) II
72
c) III
d) IV
e) V
Answer: A
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
165) For which of the following substances, C9H10O, would the aromatic multiplet, in its 1H
NMR spectrum, consist of two doublets?
O
O
O
I II III
HO
O
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
166) In the 1H NMR spectra of which of the following substances, C9H10O, would you expect to
see two singlets in the range of δ 2.0-2.5 ppm?
73
O
O
O
I II III
HO
O
IV V
a) I and III
b) I, II, and III
c) IV
d) V
e) All of these substances would exhibit two singlets δ 2.0-2.5 ppm in their 1H NMR spectra.
Answer: B
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Medium
167) Which isomer of C7H7Cl exhibits strong IR absorbances at 690 and 750 cm1?
Cl
Cl
I II III IV
a) I
b) II
c) III
d) IV
e) II and IV
Answer: E
Topic: Spectroscopy
Section: 14.11
Difficulty Level: Hard
74
a) Br2, CCl4
b) KMnO4, OH−, H2O
c) NMR Spectroscopy
d) UV Spectroscopy
e) Two of these choices.
Answer: E
a) Br2, CCl4
b) KMnO4, OH−, H2O
c) NMR Spectroscopy
d) NaBH4, H2O
e) Two of these choices.
Answer: C
170) A compound that reacts like an alkane, alkene, alkyne, or one of their derivatives, is called
an ___ compound, while one that reacts like benzene is called an ___ compound.
75
171) Humans do not have the biochemical ability to synthesize the benzene ring. Therefore, two
amino acids, ___ and ___, are essential to the human diet.
172) Cagelike molecules with the geometry of a truncated icosahedron are called ___.
Answer: fullerenes
173) Monocyclic compounds with alternating single and double bonds are called ___.
Answer: annulenes
174) The difference between the amount of heat actually released upon hydrogenation of
benzene and that calculated on the basis of the Kekule structure is called the ___ of benzene.
Answer: degenerate
76
Difficulty Level: Medium
Answer: phenyl
Topic: Nomenclature
Section: 14.2
Difficulty Level: Easy
OH
Br
Answer: O2N
Topic: Nomenclature
Section: 14.2
Difficulty Level: Medium
NH2
Br
Answer:
Topic: Nomenclature
Section: 14.2
Difficulty Level: Medium
O2N O
Answer: I
77
Topic: Nomenclature
Section: 14.2
Difficulty Level: Medium
Topic: Nomenclature
Section: 14.2
Difficulty Level: Hard
HO
HO2C
Answer:
Topic: Nomenclature
Section: 14.2
Difficulty Level: Hard
Answer: 4n+2
78
183) The heats of hydrogenation for cyclohexene and benzene are given below. Calculate the
resonance stabilization energy of benzene.
Answer: The resonance stabilization energy of benzene is the difference between the theoretical
and observed ΔHo values.
Hydrogenation of three double bonds should release 3 times the energy released when one
double bond is hydrogenated. Thus, the theoretical ΔHo for benzene can be calculated as [3x (-
120)] kJ/mol = -360 kJ/mol
Therefore,
Resonance stabilization energy of benzene = (-208) – (-360) kJ/mol
= 152 kJ/mol
184) Use the “polygon-in-circle” method to draw an MO diagram showing the pi-electron
distribution pattern in the cyclopentadienyl anion. How is this diagram useful in explaining the
aromatic properties of this anion?
Answer: The following MO diagram can be generated using the polygon-in-circle method. The
six pi electrons of the cyclopentadienyl anion in the bonding molecular orbitals form a closed
bonding shell, accounting for its aromatic properties.
Antibonding MO
Bonding MO
6 pi electrons
"closed bonding shell"
185) Use the “polygon-in-circle” method to draw an MO diagram showing the pi-electron
distribution pattern in the cyclopentadienyl cation. How is this diagram useful in explaining the
antiaromatic properties of this anion?
79
Answer: This MO diagram can be generated using the polygon-in-circle method. The 4 pi
electrons of the cyclopentadienyl cation in the bonding molecular orbitals form a bonding shell
which lacks 2 pi electrons from being closed, accounting for its antiaromatic properties.
186) Use the “polygon-in-circle” method to draw an MO diagram showing the pi-electron
distribution pattern in the cycloheptatrienyl cation. How is this diagram useful in explaining the
antiaromatic properties of this anion?
Answer: This MO diagram can be generated using the polygon-in-circle method. The six pi
electrons of the cycloheptatrienyl cation in the bonding molecular orbitals form a closed bonding
shell, accounting for its aromatic properties
H
H H Aromatic
anion
80
H H
H
B:-
188) Benzene, while unusually unreactive with electrophiles, will react under certain conditions.
However, when it does react, it does so by ___ rather than by addition.
Answer: substitution
189) Explain briefly why cyclopentadiene readily reacts with strong bases.
Answer: The acidity of a substance can be often be correlated with the stability of its conjugate
base: substances that have exceptionally stable conjugate bases tend to be strong acids. The
conjugate base of cyclopentadiene, formed during reaction with a base, is exceptionally stable,
by virtue of being an aromatic anion (6 pi electrons, planar ring), thus accounting for the
readiness with which cyclopentadiene reacts with bases.
B:−
..
H
H H Aromatic
anion
81
H H
H
+ Ph3C+ + Ph3CH
Answer: This reaction readily proceeds because the product, cycloheptatrienyl cation, is aromatic
and much more stable than even the triphenyl substituted carbocation.
191) Pyrrole is not particularly basic, because the lone pair on the nitrogen is ___.
192) The Lewis structures of both pyridine and pyrrole have an electron pair on the nitrogen
atom, suggesting that both substances might possess basic properties. However, only pyridine
reacts readily with HCl to form pyridinium chloride, while pyrrole is rather unreactive. Explain
clearly, using relevant diagrams to illustrate/clarify your answer.
Answer:
+ HCl
N N+ −
.. Cl
2 H
sp
pyridinium chloride pyridinium chloride
.. p
H
N H + HCl X N + Cl−
H
82
reacting with HCl, forming pyridinium chloride, while preserving aromatic stability.
By contrast, the electron pair in pyrrole must be placed in the p orbital, since all three sp2 orbitals
are used in sigma bonds with neighboring atoms. This allows the electron pair to contribute to
aromatic stability by becoming part of the aromatic sextet. Thus, the electron pair on nitrogen is
not “available” for reacting with HCl, because doing so would destroy the aromaticity of the
ring.
193) Predict the product of the reaction of one equivalent of hydrochloric acid with the organic
compound shown:
H
N
1 equivalent HCl
Answer:
H H
N N
1 equivalent HCl
N N
194) Consider the nitrogen atom in the molecules of pyrrole and pyrrolidine. Bearing in mind
that pyrrole exhibits aromatic properties, compare the hybridization of nitrogen in both species,
explaining why it must be different, although at first glance, it may appear identical.
H H
N N
pyrrole pyrrolidine
Answer:
83
sp2 sp3
NH NH
In pyrrole, the conjugated unsaturated ring system forces the nitrogen to be trigonal planar, that
is sp2 hybridized, with the lone pair electrons in an unhybridized p-orbital. This allows for
overlap with the conjugate system accounting for the aromatic character. The nitrogen in
pyrrolidine, on the other hand, is closer to tetrahedral, and as a result sp3 hybridized, and the lone
pair electrons reside in an sp3 hybrid orbital.
195) Briefly explain why the aromatic hydrocarbon shown possesses a significant dipole
moment. Use diagrams as needed to illustrate/clarify your answer.
Answer:
+
=
The stable, low energy resonance contributor shown creates an aromatic system in both rings.
This separation of charge creates the significant dipole observed.
Topic: Aromaticity
Section: 14.7
Difficulty Level: Hard
196) Briefly explain why the aromatic hydrocarbon shown possesses a significant dipole
moment. Use diagrams as needed to illustrate/clarify your answer.
84
Answer:
The stable, low energy resonance contributor shown creates an aromatic system in both rings.
This separation of charge creates the significant dipole observed.
Topic: Aromaticity
Section: 14.7 and 14.8
Difficulty Level: Hard
197) Briefly explain why the aromatic hydrocarbon azulene, C10H8, possesses a significant
dipole moment. Use diagrams as needed to illustrate/clarify your answer.
Answer: Azulene has the bicyclic structure shown below. Since the “non-polar” resonance
hybrid meets the Hückel rule for aromaticity, it accounts for the observed aromatic properties of
azulene. However, closer scrutiny suggests that a shift in electron density, in which the 7-
membered ring is electron deficient and the 5-membered ring is electron-rich would be
especially stable: each ring is now independently aromatic, an aromatic cycloheptatrienyl cation
fused with an aromatic cyclopentadienyl anion. Thus, the most stable pi-electron distribution
would suggest a polar structure for azulene, accounting for this substance having a significant
dipole moment.
non-polar polar
Topic: Aromaticity
Section: 14.7
Difficulty Level: Hard
198) Although all bond lengths in benzene are identical, that is not always true for all aromatic
compounds. In naphthalene, for instance, the C1-C2 bond is shorter than the C2-C3 bond.
Explain, using resonance theory.
85
Answer: The major resonance structures for naphthalene are drawn below. The observed bond
lengths reflect the contribution of each structure to the overall resonance hybrid:
The C1-C2 bond: two double bonds (I and II), and one single bond (III)
The C2-C3 bond: one double bond (III), and two single bonds (I and II)
Overall: C1-C2 bond is more double-bond-like, thus shorter.
shorter
1 1 1 1
2 2 2 2
longer
3 3 3 3
I II III IV
Answer: ..N N
..
Topic: Resonance
Section: 1.8 and 14.9
Difficulty Level: Hard
Answer:
Topic: Resonance
Section: 1.8 and 14.8
Difficulty Level: Hard
201) Draw all significant resonance structures for the cyclopentadienyl anion.
Answer:
86
202) Consider the oxygen atom in the molecules of furan and tetrahydrofuran. Bearing in mind
that furan exhibits aromatic properties, compare the hybridization of oxygen in both species,
explaining why it must be different, although at first glance, it may appear identical.
.. ..
O.. O.
.
Furan THF
Answer:
.. p 3
2 .. sp
O .. sp O
.. sp3
Oxygen has 2 lone electron pairs in both species and, at first glance, it might appear that the
hybridization patterns are identical. In THF, the oxygen atom is sp3 hybridized and both pairs
can be placed in sp3 hybrid orbitals. In furan, there are two possibilities that must be considered:
i) the oxygen may be sp3 hybridized, with both electron pairs sp3 hybrid orbitals, as in THF, or,
ii) oxygen may be sp2 hybridized, with one electron pair in an sp3 hybrid orbital, the other in a p
orbital. In the latter case, the electrons in the p orbital can then become part of an aromatic
sextet, allowing the molecule to gain aromatic stability. Since furan is known to exhibit markedly
aromatic properties, the oxygen must be sp2 hybridized.
Topic: Resonance
Section: 1.8 and 14.8
Difficulty Level: Hard
203) The compound illustrated below is found to have the following signals in its broadband
decoupled C-13 spectra:
Using resonance theory, assign the C-13 peaks to the appropriate carbons.
87
CHO
Cl
Answer:
190.77 CHO
134.82
130.89
129.45
140.91
Cl
88