Chemistry II (Organic): Heterocyclic Chemistry

TUTORIAL PROBLEMS
Prof Alan Spivey; Office: 835 C1; e-mail: a.c.spivey@imperial.ac.uk; Tel.: 45841
1. Draw the following heteroaromatic structures and give at one alternative tautomeric structure
for each:
(a) 1-hydroxyisoquinoline
(b) 3-aminoquinoline
(c) 2-hydroxyfuran
(d) 4-hydroxypyridine
(e) 2-aminothiophene

2. Show how Huckel’s rule is in accord with MO energy diagrams of:

(a) pyridine
(b) furan

3. Nitration of pyridine using a mixture of c.H2SO4 and c. HNO3 at 300 °C results in 10%
conversion to 3-nitropyridine in 24 h. By contrast, treatment of pyridine-N-oxide under milder
conditions for 4 h furnishes 4-nitropyridine-N-oxide in 90% yield:
c.H2SO4:c.HNO3 (1:1) NO2
NO2 c.H2SO4:c.HNO3 (1:1)
300°C, 24h
[10%] 90°C, 4h [>90%]
N N N N
O O

(a) provide a mechanism for the reaction of pyridine and account for the regioselectivity
observed.
(b) explain why the N-oxide displays higher reactivity in this type of reaction and gives
different regioselectivity compared to pyridine.

4. Give reasonable mechanisms for the following transformations:

(a)
Me H (cat)
Me heat Me
O + O
HO O
Me Me
Me
Me

(b) Me O H (cat) EtO 2C Me

EtO 2C
+ heat
Me O EtO 2C NH2 Me N CO2Et
H
NO2
NO2
O2N NH3
(c) O O heat HNO3
EtO 2C +
EtO 2C CO2Et
Me EtO 2C CO2Et
Me N Me
H Me N Me

5. Provide the missing reactant for each of the following transformations and draw out a
mechanism.

(a) Me

NH2 Me
N N
Me Me
O O
(b) O O
S N
S Ph O
Ph
N
O Ph Ph