Chemistry 202-102
Test # 2
February 25, 2010
Dr. Richard Rogers
Name: _________________________________________
1. Label the following compounds as to whether they are aromatic (A), non-aromatic
(NA), or antiaromatic (AA). (10 points)
CH3
B
CH3
N
O
N
O
NH
C
C C
N
S
2. Label the following reactions as to whether they will occur easily (OE), or occur with
difficulty (OWD). (9 points)
+
t-Bu- Li+
HCl
N
H
N
H H
Cl
HCl
N
N
H
N
H
Cl
N
H
1
3. 1-azacycloheptatriene is stable at room temperature. Circle each true statement. (12
points)
NH
a. The compound is basic.
b. The compound will add bromine across the double bonds.
c. The compound will easily loose a proton to a base.
d. The compound is planar.
e. The nitrogen is sp3 hybridized.
f. The compound is antiaromatic.
g. The compound is non-planar.
h. The compound is non-aromatic.
4. Draw the structure of the following compounds (6 points).
a. 3-chloro-4-cyano-6-methylphenol
b. 3-(N,N-dimethylamino)-5-propylnitrobenzene
5. List the following compounds according to the rate at which they will undergo
bromination in the presence of an appropriate catalyst: slowest (1) to fastest (2). (6
points).
NO2
CH3
OH
H
O
Cl
2
6. For the nitration of methyl benzoate, draw the sigma complex (the reactive
intermediate) which results from attack at the ortho, the meta, and the para positions. For
each sigma complex, draw all appropriate resonance structures. Circle any “high energy”
resonance structures. (15 points).
O
O
+ HNO3
O
O
+ HNO3
O
H2SO4
H2SO4
O
+ HNO3
H2SO4
3
7. Using appropriate resonance structures show atoms with high electron density for Nmethyl acetanilide (12 points).
CH3 CH
3
N
O
8. Draw the product and all appropriate resonance structures for the reaction shown
below (6 points).
H
NaH
H
b. For the above product, how many peaks would one see in the 13C NMR (2 points)?
c. For the above product, how many peaks would one see in the 1H NMR (2 points)?
4
9. Show the main product which would result from the following reactions (16 points).
OH
H2SO4
+
Cl
H2SO4
HNO3
+
CH3
O
+
AlCl3
CH3I
xs
Cl
AlCl3
Cl
+
xs
O
+ KMnO4
NaOH
H2O/100o
CH3
+ NBS
hν
Br
O
+
NaNH2
Br
5
Cl
+
CH3O- Na+
Cl
N
CH3OH
Reflux
10. Show how you would synthesize one of the following compounds starting with
benzene. You may use any acylic or inorganic reagent of your choosing (10 points).
OH
O
OH
NH2
CH3
NO2
Br
Cl
6