Nomenclature of
Heterocyclic
Compounds
The IUPACrules allow threenomenclatures.
I. The Hantzsch-Widman Nomenclature
II. CommonNames
III. The Replacement Nomenclature
I. Hantzsch-Widman Nomenclature
n = 1,2,3, ……
The Hantzsch-Widman nomenclature is based on the type
(Z) of the heteroatom; the ring size (n) and nature of the
ring, whether it issaturated or unsaturated .
This system of nomenclature applies to monocyclic three-
to-ten-membered ringheterocycles.
I. Type of the heteroatom
The type of heteroatom is indicated by a
prefix as shown below for common
hetreroatoms:
Hetreroatom Prefix
O Oxa
N Aza
S Thia
P Phospha
II. Ring s ize (n)
The ring size is indicated by a suffix according to Table I
below. Some of the syllables are derived from Latin
numerals, namely ir from tri, et from tetra, ep from
hepta, ocfrom octa, on from nona, ecfrom deca.
Suffix to indicate ring size
Ring size Suffix Ring size Suffix
3 ir 7 ep
4 et 8 oc
5 ol 9 on
6
rese in SCH 40 2 10 ec
The endings indicate the size and degree of
unsaturation of the ring.
Table II: Indicate the ring size and degree of unsaturation
of heterocycles
Ringsize Saturated Unsaturated Saturated (With Nitrogen)
3 -irane -irine -iridine
4 -etane -ete -etidine
5 -olane -ole -olidine
6 -inane -ine
7 -epane -epine
8 -ocane -ocine
9 -onane -onine
10 -ecane -ecine
According to this system heterocyles are named by
combining appropriate prefix/prefixes with a stem from
Table II. The letter “a” in the prefix is omitted where
necessary.
Each suffix consists of a ring size root and an
ending intended to designate the degree of
unsaturation in the ring.
It is important to recognize that the saturated suffix
applies only to completely saturated ring systems, and
the unsaturated suffix applies to rings incorporating the
maximum number of non-cumulated double bonds.
Systems having a lesser degree of unsaturation
require an appropriate prefix, such as
"dihydro"or"tetrahydro".
Saturated 3, 4 & 5-membered nitrogen
heterocycles should use respectively the
traditional "iridine", "etidine" and "olidine"
suffix.
Examples
Oxa+irane= Oxirane Thia+irane= Thiirane Aza+iridine= Aziridine
Oxa+etane=Oxetane Thia+etane=Thietane Aza+etidine=Azetidine
Oxa+olane= Oxolane Thia+olane= Thiolane Aza+olidine= Azolidine
Azinane Azine
Pyridine
In case of substituents, the heteroatom is designated
number 1, and the substituents around the chain are
numbered so as to have the lowest number for the
substituents.
The compound with the maximum number of
noncumulative double bonds is regarded as the
parent compound of the monocyclic systems of a
givenring size.
Partial Unsaturation
Use fully unsaturated name with dihydro, tetrahydro, etc
3
2
1
HN
Azepine 2,3-Dihydroazepine
4,5-Dihydroazepine 2,5-Dihydroazepine
When numbering give priority to saturatedatoms.
1-Ethyl-4-methyl-4,5-dihydroazepine
N
1-Ethyl-5-methyl-2,3,4,5-tetrahydroazepine
N
Ringswith More Than OneHeteroatom
Two or more similar atoms contained in a ring are
indicated bythe prefixes ‘di-’, ‘tri’, etc.
1,3,5-Triazine
If more than one hetero atom occur in the ring, then the
heterocycle is named by combining the appropriate
prefixes with the ending in Table I in order of their
preference, O>S> N.
1,3-Thiazole
Oxaziridine
(Thiazole)
1,4-Oxazine 3-chloro-5-methyl-1,2,4-oxadiazole
Priority of heteroatoms for numberingpurposes:
Highest
C N O
B
Lowest P S
Se
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. As a
result the position of the substituent plays no part
in determining how the ring is numbered in such
compounds.
4-Methyl-1,3-thiazole
II. CommonNames
There are a large number of important ring
systems which are named widely known with their
non-systematic or common names.
H
O N
Furan Pyrrole
N
O O
Isoquinoline Coumarin
Pyridine 1,4-Dihydropyridine 2,3-Dihydropyridine
Identical systems connected by a single bond
Suchcompoundsare defined bythe prefixes bi-, tert-
, quater-, etc., according to the number of systems, and the
bonding is indicated as follows:
1 1
2’ 2’
2 4’
2 3’’ 1’
1’ 2’’
1’
2,2' - Bipyridine 2,2': 4',3'' -Terthiophene
Naming Hetrocycles with fused rings
When naming such compounds the side of the heterocyclic
ring is labeled by the letters a, b, c, etc., starting from the
atom numbered 1. Therefore side ‘a’ being between atoms 1
and 2, side ‘b’ between atoms 2 and 3, and so on as shown
below for pyridine.
c d
b e
a f
The name of the heterocyclic ring is chosen as the
parent compound and the name of the fused ring is
attached as a prefix. The prefix in such names has
the ending ‘o’, i.e., benzo, naphtho and so on.
b b c
a
a a b
Benzo [b] furan Benzo [c] thiophene
Benzo [b] pyridine
d Benzo [d] thiepine
a
c
b
In a heterocyclic ring, other things being equal, numbering
preferably commences at a saturated rather than at an
unsaturated heteroatom.
1 2 1
HN N N
N2
3-Ethyl-5-methylpyrazole 1-Methylindazole
Handling the “Extra Hydrogen”
Heterocycles with maximum number of double bonds which can
be arranged in more than one way.
Examples
Pyrans
Double bonds @ Double bonds @
3 and 5 2 and 5
Double bonds @ Double bonds @
2 and 4 1 and 3
Pyrroles
Double bonds @
1 and 4
Therefore, should have different names.
This is a special problem resulting from isomerism in the position of
the double bonds which is sometimes referred to as “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 atom.
4
2 3
1 1 2
2H-Pyran
4H-Pyran
The saturated position takes priority in numbering.
43
1H-Pyrrole 3H-Pyrrole 2H-Pyrrole
(Pyrrole)
2 4 3
3
1 2
1 4
4-Methyl-2H-oxetene 2-Methyl-2H-oxetene
III. The Replacement Nomenclature
In replacement nomenclature, the
heterocycle's name is composed of the
carbocycle's name and a prefix that denotes the
heteroatom.
Thus, "aza", "oxa", and "thia" are prefixes for a
nitrogen ring atom, an oxygen ring atom, and a
sulfur ring atom, respectively.
Notice that heterocyclic rings are numbered so that
the heteroatom hasthe lowest possible number.
NH N
2-Methylazacyclohexane
or N-Ethylazacyclopentane
2-Methylpiperidine or
N-Ethylpyrrolidine
