name ______________________________
Page 1 of 6
1-10. Multiple Choice. Provide the best answer for each question. There is only one answer for each
question. (3 pts each, 30 pts total)
1.
Which of the following is NOT a resonance structure for benzene?
a)
2.
b)
c)
d)
Which of the following would you expect to be the major product from the nitration of
4-bromobiphenyl?
HNO3, H2SO 4
Br
a)
b)
O2N
Br
NO2
Br
d)
NO2
c)
There will be NO reaction
Br
3.
Which of the following would NOT be a product from the Friedel-Crafts alkylation of benzene with
1-bromopropane?
a)
b)
c)
d)
a, b and c are all possible products
for the reaction
4.
Which of the following does NOT contain a conjugated system.
a)
O
b)
H3C
5.
c)
d)
CH3
N
CH3
Which of the following reagents will react with (R)-2-octanol to give an optically active product.
a)
b)
PBr3
c)
SOCl2
d)
TosCl
a, b, and c will all give an
optically active product
name ______________________________
Page 2 of 6
6.
The pKa of phenol is 10. Which of the following compounds would you expect to be LESS acidic
than phenol?
a)
b)
OH
c)
OH
d)
OH
SH
NO2
C
N
7.
NH2
Which of the following compounds is aromatic?
a)
b)
c)
+
d)
N
None. i.e., a, b and c are
not aromatic compounds
O
8.
Which of the following compounds is anti-aromatic?
a)
9.
b)
+
c)
d)
Which of the following oxidants can be used to convert 1-hexanol to hexanal?
O
[O]
OH
H
1-hexanol
a)
b)
PCC
10.
_
hexanal
CrO3, H3O+
c)
d)
KMnO4
a, b, and c will all give the
hexanal as the major product
Which of the following compounds is predicted to undergo electrophilic aromatic nitration the
slowest?
a)
C
N
b)
OCH3
c)
d)
Compounds a, b, and c would
undergo nitration at
approximately the same rate
name ______________________________
Page 3 of 6
11.
Anthracene is shown below. There are a total of four resonance structures for anthracene. Draw the
remaining three resonances structures and draw curved arrows showing how the resonances
structures can be interconverted. (12 pts)
12.
Answer the following questions concerning the cycloheptatrienyl cation (also known as the
tropylium ion), shown below. (12 pts)
+
a) How many conjugated p-orbitals does the tropylium ion have? 2 pts
7
b) According to Hückel, is the tropylium ion aromatic? Explain briefly although precisely Hückel
criteria for aromaticity? 4 pts
Yes: According to Hückel, aromatic systems have 4n+2 π-electrons, where n is an
integer. The tropylium ion has 6-π-electrons which follows Hückel's criteria
c) Draw a molecular orbital diagram of the tropylium ion showing the relative energies of the MO's
and where the electrons are. You do not need to draw the phases of the individual orbitals. 8 pts
NB
+
13.
name ______________________________
Page 4 of 6
From the list below, provide the proper reagents, needed to complete the following reactions. (3 pts
each, 18 pts total)
A.
B.
C.
D.
E.
F.
G.
H.
Br2, FeBr 3
HNO3, H 2SO4
SO3, H 2SO4
I2, CuCl 2
Cl2, FeCl 3
KMnO4
NBS, peroxides, ∆
H2, Pd/C
I. NaOH, 300 °C
J. 1. LiAlH4 2. H3O+
K . 1. NaBH4 2. H3O+
L. 1 Hg(OAc)2, H 2O 2. NaBH 4
M. 1. B 2H6 2. H2O2, NaOH, H2O
N . PBr3
O. CrO3, H 3O+
P . PCC
O
OH
OCH3
J
O
H
A
Br
Br
G
OH
SO3H
H3C
O
I
H3C
OH
O
OCH3
O
K
OCH3
14.
name ______________________________
Page 5 of 6
Give the major product for the following reactions (9 pts).
O
OCH3
H3C
Cl
Cl
1) H3C-MgBr
(excess)
O
OCH3
HO
2) H3O+
(H3C)3SiCl,
(CH3CH 2)3N
O
15.
OCH3
AlCl3
Cl
HO
O
O
(CH 3)3Si
H
O
H
Starting from benzene, any alkyl halide, any acid chloride and any necessary reagents, synthesize
4-chloro-2-nitroaniline. (10 pts)
NO2
HNO3, H2SO4
Cl2, FeCl3
NH2
Cl
H2, Pd/C
-orSnCl2
HNO3, H2SO4
NH2
NH2
NO2
Cl
name ______________________________
Page 6 of 6
16. Provide a structure consistent with the following spectroscopic data.
Formula: C8H9OCl
IR: broad absorption from 3600-3400 cm-1
13C NMR: δ 138, 131, 129, 127, 65, 39
1H
NMR: δ
4 degrees of unsaturation
-OH group present
138, 131, 129, 127:
4 aromatic 13C peaks=
p-disubstituted benzene
7.50 d, J= 9.0, 2H
7.10 d, J= 9.0, 2H
p-disusbtituted benzene
3.70 t, J= 5.0, 2H
-CH 2 -CH 2 -
3.00 s, 1H
perhaps an O-H
2.70 t, J= 5.0, 2H
-CH 2 -CH 2 -
in the O-C-H
region
in the Ar-CH
region
Data is consistent with the following two structures:
OH
Cl
Cl
HO
____________________________________________________________________________________
Problem
1-10:________
(30 pts)
14:________ (9 pts)
11:________
(12 pts)
15:________ (10 pts)
12:________
(12 pts)
16:________ (9 pts)
13:________
(18 pts)
Total out of 100: _________