Organic chem. IV.

BCH 2210

CAT 1 AND II

INSTRUCTIONS: 1. Answer ALL questions in section A (40 Marks)

2. Attempt any ALLquestions in section B (60 marks)

SECTION A: Attempt All questions (40 Marks)

1. Account for the aromatic character of pyridine using both the molecular orbital theory
and resonance theory. (6 Marks)
MOT
This can be explained by the fact that nitrogen is sp2 with two of the tree
sp2 forming overlaps with sp 2 of the neighboring carbon atoms and the
third nitrogen pair has the lone pair. The unhybridized p orbital contains a
single electron, which is part of the 6 pi-electron system delocalized
around the ring.
Resonace Theory
The molecule contains delocalized 6 pi electrons that are in a conjugated
manner. These pi electrons can appear arbitrarily on any bond as long as
they conjugated thus conforming to the rules aromaticty

2. Name the following compounds systematically. (2 marks each)

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 O
N
a) S
b)

N
S

H
N Br
c) N
N d) Br
N
N

H N
CH3
N
e)
f)
HN NH
S

a)Thiazole

b) 4-bromo-1,2,5-oxathiazine

c)1,2,3,5 tetraozle

d) 5 Bromo-2-methyl-1,3-diazine

e)1,3,5-triazane

f)benzo[b}thiophene

3. Write the structures for the following compounds. (2 marks each)

a) Oxolane

b) Pyrrolidine

c) 2-Chloro-5-methylpyridine

d) 5-Ethyl-1,3-diazole

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e) 3-Methoxythiepin

f) 3H-Azepine

g) 3-Acetyl-2-bromobenzo[b] thiophene

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4. Account for the aromaticity of furan, pyrrole and thiophene using both the molecular
orbital and resonance theory. (8 Marks).

Pyrrole has lone pair of electrons with are found in the in the 2p orbital which are found
to overlap in the pi bonding system thus we have six pi electrons. Thus we have three pi
bonding molecular orbitals and two antibonding molecular orbitals. The bonding
molecular orbitals are fully filled while other is empty. Thus contributing six electrons in
the molecule which supports the rules aromaticity.

Resonance theory. Electrons found in the lower energy antibonding molecular orbital
contribute to the aromatic character due to the conjugation of the pi electrons. Two
electrons of pyrrole found in the 2p and in the pi bonding system don’t take part in
bonding.

Furan just like pyrrole the oxygen in furan has 2 lone pairs found in the pi bonding
system while the others are found in the sigma orbital. Therefore we have 6 pi electrons
which satisfy the law of aromaticity of cyclic molecules. Two electrons of furan found in
the 2p and in the pi bonding system don’t take part in bonding

Resonance theory since this pi electrons are found with in the same molecular orbital. A
molecule with delocalized electrons tends to be more stable Furan is least stabilized
compared to thiophene since oxygen is more electronegative. Thus it will tend to pull
electrons towards itself than facilitate delocalization

Thiophene.

Thiophene is aromatic because it has six pi electrons in a planar, cyclic, conjugated

system. Sulfur atom re-hybridizes to sp2, it will have an electron pair in a 3p orbital that
can overlap with the carbon 2p orbitals on either side.

Resonance Structure

This give a planar, cyclic conjugated system that contains six electrons, The sulphur in
has lower resonace energy compared because 3p orbital of S is bigger than the 2p orbitals
on c. so the orbital overlap in a less effective manner.  The lone pair of Sulphur
delocalises easily, and so aromatisation is better.

SECTION B: Attempt any 3 questions

Question one

a) Show the step by step mechanism description of how pyrolle ring in presence of strong
acids undergoes protonation and then polymerization? (6 Marks)
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b) Show the step by step mechanism description of how furan ring in presence of mild acids
opens up to form 1, 4- dicarbonyl compounds? (6 Marks)

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c) By help of mechanism reaction steps, explain why electrophilic substitution in five
membered heterocyclics at 2 or 5 positions is more preffered than 3 or 5 positions? (8
marks)

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Question two

By help of examples give ten (10) heterocyclic molecules that are useful in day to day life
and briefly describe their uses. (20 marks)

Niacin

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Niacin is a B vitamin that's made and used by your body to turn food into energy. It helps
keep your nervous system, digestive system and skin healthy.

Strychnine

Its is plant alkakoid highly toxic that is used as a pesticide that is widley used in killing
rodents.

Ibogaine

This an alkaloid found in stems of and roots of African shrub Tabernathe iboga. It’s a
psychedelic that has found use in treatment of opioid withdrawal cravings.

Furfual is an oil ,that is light sensitive when exposed to air. It is used as a solvent in the
refinery of oils and as herbicide and fungicide.

Indozole

It’s a rare heterocyclic, but this particular nulcleus in a variety of synthetic compunds, has a
wide range of pharcological activities such as anti-inflammatory, antiarrhythmic, antitumor,
antifungal antibacterial and anti HIV activities.

5-Meo-DMT

5-Methoxy-Dimethyltryptamine that occurs natural product found in parotid gland secretions

of the toad. Research has found that the it has some efficacy in treating desperssion.

Furan

Furan is used in the formation of lacquers and solvents in the making of epoxy. I has also
wide application of agricultural chemicals insecticides and stabilizers and pharmaceuticals
products.

Pyridine

Pyridine is used as a solvent and to make many different products such pharmaceuticals ,
paints, food flours, dyes, rubbers and adhesives.

Histidine

It is an amino acid: used to make proteins and enzymes in the body,  with unique roles in
proton buffering, metal ion chelation, scavenging of reactive oxygen and nitrogen species,
erythropoiesis, and the histaminergic system.

QUINOLINE

Quinolone is used in the manufacture of dyes, the preparation of hydoxyquinoline . Its found
in as solvent for resins and other specialty chemiclas.

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Question three

a) Explain why electrophilic substitution in pyridine takes place at meta positions only
and not ortho and para positions. (10 Marks)

Electrophilic substitution looks likely to take place in all positions. However the position
is highly favored is the meta position. During the intermediate the positive charge does
not fall on the nitrogen in the three resonance forms.

b) Explain why nucleophilic substitution in pyridine takes place at ortho and para
postions only and not meta positions. (10 Marks)

Nitrogen is generally effective in nucleophilic substitution due to the carbon double bond
with nitrogen. There are effective as due to the electronegative atom hence there have
electron with drawing in their structure. The negative charge is present on the nitrogen
hence facilitates stabilization from the eletronegativity of nitrogen

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Question four

a) Explain why the stabilities of furan, pyrrole and thiophene are different. Which is the
most stable and least stable ring system? (6 Marks)
b) Give the structures of the major products A to G formed from the following reaction
sequences. (2 marks each)

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 H2O, HOAc
a) A
Heat
Me O Me

b) Ac2O
B
Heat
N
H

c)
i) NaNH2
C
PhNMe2
100oC
N ii) H2O

HOAc, H2O2

70-800C

HNO3 / H2SO4 Fe / HOAc

D E F
900C

d)

+ Heat
G
O O
O
O

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