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EXERCISES
HETEROCYCLIC AROMATIC COMPOUNDS

1 Give the resonance structures for the intermediate in the reaction of 4-chloropyridine with
ammonia.
Answer :

Cl NH2 Cl NH2 Cl NH2

- -

N N N

2. Draw resonance structure of the intermediates for nitration at the 5- and 6-positions of quinoline
to show why 5-nitroquinoline is formed preferentially.
Answer :

H NO 2 H NO 2 H NO 2
+
+

N + N N

H NO2 H NO 2 H NO 2
+

N N +
N
+

NO 2 NO 2 NO 2
H + H H
+
+
N N N

NO 2 NO 2 + NO 2
H H H +

+
N N N

The 5-intermediate has three resonance structures with one aromatic ring, while the 6-
intermediate has only two.

3 If pyrrole did form a cation when treated with HCl, what would its structure be ?
(Show the p orbitals). Would the pyrrole cation be aromatic or not ?
Answer :

sp3

or
atau + not aromatic
tidak atomatik
+ NH2
N
H H

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4. Predict the major organic monosubstitution products :

BF3
a. furan + (CH3CO)2O
25°
b. thiophene + H2SO4
25°
c. pyrrole + C6H5N2+ Cl–
dioksana
d. furan + Br2
25°
Answer :
O
a. CCH3 b. SO 3H
O S

c. N=NC6H5 d. Br
N O
H

5. When atropine is subsjected to acid hydrolysis, two products can be isolated : tropine, which is
not optically active, and tropic acid, which is obtained as a racemic mixture. What are the
structures of these two compounds ?
Answer :

NCH3

+ HO 2CCHCH2OH
C 6H5
H
OH
tropine tropic acid

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6. Write equations showing the mechanism of the following conversion, shown at the start of the
synthetic sequence.
C2H5O2CCH2CH2NHCO2C2H5 + trans-C2H5O2CCH=CHCO2C2H5 → B
Answer :
H
O
C2 H 5 O 2 C COC2 H5

CO2 C2 H5 CO2 C2 H5 Michael

Na H
-
NHCO2 C2 H5 N
CO2 C2 H5

O
C2 H 5 OC CH O C2 H 5 O 2 - transfer
proton
C2 H 5 O 2 C CH C C2 H 5 O 2 C CHCHCOC2 H 5 proton
transfer
N OC2 H5
N
CO 2 C2 H 5 CO2 C2 H5
O
C2 H 5 O 2 C O
C2 H 5 O 2 C CHCH2 CO2 C2 H5 _ - OC2H 5
Dieckmann C2 H 5 O
-
HC: N CO2 C2 H5
CO 2 C2 H 5 C2 H 5 O 2 C
N
CO 2 C2 H 5
O O

CO2 C2 H5 - H+ CO2 C2 H5
C2 H 5 O 2 C C2 H 5 O 2 C -
N N
CO 2 C2 H 5 CO 2 C2 H5

B anion
anionofB B

7. Give the structures and show the hydrogen bonding between uracil and adenine.
Answer :

O H2N N

NH N NH
N
H O