HETEROCYCLIC COMPOUNDS

What is meant by heterocyclic

compounds?
A heterocyclic compound is one
which possesses a cyclic structure with
at least two different kinds of atoms in
the ring.
Why we study heterocyclic
chemistry?
Heterocyclic chemistry is a
large and important branch of
organic chemistry. Heterocyclic
compounds are very widely
distributed in nature, and are
essential to life in various ways.
Heterocycles are divided into:
Aliphatic heterocycles, e.g. piperidine and
pyrrolidine,
CH3 CH3
CH2 CH2
N N N
H
H H

piperidine Pyrrolidine diethylamine

Aromatic Heterocycles are related to the
fundamental aromatic carbocyclic systems
e.g. benzene, cyclopentadienyl anion, ... etc
by replacement of one or more-CH= with
heteroatoms. Aromatic heterocycles (or
heteroaromatics) are the most important
heterocycles and this study will be
concentrated on them.

N
Nomenclature of Heterocyclic compounds

1- Trivial names: In the early days of

organic chemistry heterocycles were given
names related to their natural source or
method of preparation, (e.g. furfural ),
properties (e.g. thiophene) or both (e.g.
pyridine).
2- IUPAC (systematic or chemical) names:
To-day, the system employed for naming
heterocycles, is given by the International
Union of Pure and Applied Chemistry
(IUPAC) and is followed throughout the
world.
IUPAC Nomenclature of Monocyclic
Heterocycles:
The following is a summary of the IUPAC
rules:
1-The IUPAC (or systematic) name consists
of one or more prefixes from table 1 with
multipliers when needed designating the
heteroatoms followed by a stem + suffix
from table 2 which give the ring size and
unsaturation. This is preceded by
substituents.
Table (1) Hantzsch-Widman system prefixes
(in decreasing order of seniority)
Element Bonding Prefix
number
(Valence)
Oxygen 2 oxa
Sulfur 2 thia
Selenium 2 selena
Nitrogen 3 aza
Phosphorus 3 phospha
Arsenic 3 arsa
Silicon 4 Sila
Boron 3 Bora
Table (2) Hantzsch-Widman system stems
Ring Unsaturated Saturated Ring Unsaturated Saturated
Size Size
3 irene/irine irane/iridine 7 epine Epane

4 ete etane/etidine 8 ocine Ocane

5 ole olane/olidine 9 onine Onane

6A ine ane 10 ecine Ecane

6B ine inane
6C inine inane
A (O, S, Se)
B (B, N)
C ( P, As, Si )
If two or more kinds of heteroatoms
occur in the same name, their order of
citation follows the sequence of seniority
in table (1).
Numbering begins with the element
highest in table (1) (i.e. O > S > N) and
continues in the direction that gives the
lowest number to the next heteroatom. .
 1
1 8 O
S 2 7 2
7
3 6 3
6
4 5 4
5

thiepane (PIN) oxocane (PIN)

Two or more similar atoms contained in a ring
are indicated by the prefixes ‘di-’, ‘tri’, etc.

N N

1,3,5-triazine
 1
N 1
2 O
5 2
3
N O3
5 4 4

1,5-diazocine 1,3-dioxolane
 1 1
S O
5 2 5 S2

4 N 3
3 4

1,3-thiazole 1,2-oxathiolane
 7 1 7 1
O O
6 O NH 2
6 S S2
5 3
5 3 4
4

1,2,6-oxadithiepane 1,6,2-dioxazepane
(not 1,3,7-oxadithiepane; (not 1,3,4-dioxazepane; not
1,3,7-dioxazepane; not 1,6,5-
the locant set ‘1,2,6 ‘ is dioxazepane; the locant set
lower than ‘1,3,7’) ‘1,2,6 ’is lower than ‘1,3,4’;
‘1,3,7’; or ‘1,5,6’)
 O O
PH S
NH

1,2-oxaphospholane 1,2,3-oxathiazolidine
O
NH
S

1,3,2-oxathiazolidine
The ring is numbered from the atom of preference
in such a way so as to give the smallest possible
number to the other hetero atoms in the ring.

1
1
5 S S
2 5 2
4 N
4 N3
3

4-Methyl-1,3-thiazole 2-Methyl-1,3-thiazole
 N 1

4 2
Cl N CH3
3

4-chloro-2-methyl-1,3-diazine
A- Unsaturated 5- membered rings:

N S O
H
Pyrrol Thiophene Furan
(1H- azole) (thiole) (oxole)

2,3-dihydro-1H -pyrrole

N
H
extra-hydrogen” and this can be addressed by
simply adding a prefix that indicates the number of the
ring atom that possesses the hydrogen using italic
capital ‘1H’ ‘2H’ ‘3H’, etc. The numerals indicate the
position of these atoms having the extra hydrogen
H
atom.
H
H

N N H N
H
1H-pyrrole 3H-pyrrole 2H-pyrrole
 N
H3C

1-methyl-1H-pyrrole
Presence of saturated atom
(indicated hydrogen)
 N N N

N S O
H

Imidazole thiazole oxazole

1H-1,3-diazole 1,3-thiazole 1,3-oxazole
 N N N
N S O
H

Pyrazole isothiazole isoxazole

1H- 1,2-diazole 1,2-thiazole 1,2-oxazole
 B- Unsaturated 6-membered rings:

N
N
N
N N N N

Pyridine Pyridazine Pyrimidine Pyrazine

Azine 1,2-diazine 1,3-diazine 1,4-diazine
 H H
H
O
H O

2H-pyran 4H-pyran
2H-oxine 4H-oxine

S S
2H-thiopyran 4H-thiopyran
2H-thiine 4 H-thiine