Heterocyclic Chemistry

N Nomenclature of Heterocyclic
S compounds
O

Heterocyclic Chemistry
Heterocyclic Chemistry
 Nomenclature of heterocyclic compounds

 There are three systems for naming heterocylic

compounds:

1) The common nomenclature: which convey little or no

structural information but it still widely used.

2) The Hantzsch-Widman (IUPAC or Systematic) method

which in contrast is designed so that one may deduce
from it the structure of the compound.

3) The replacement method

Heterocyclic Chemistry
 I-Common Nomenclature
 Each compound is given the corresponding trivial name (which
should be memorized, see the following slides). This usually
originates from the compounds occurrence, its first preparation or its
special properties.

 If there is more than one hetroatom of the same type

numbering starts at the saturated one, e.g. imidazole.
4 N3

5 2
1
N
H
 If there is more than one type of the heteroatoms, the ring is
numbered starting at the hetroatom of the higher priority (O>S>N)
and it continues in the direction to give the other hetroatoms the
lower numbers as possible.

Heterocyclic Chemistry
 Common Nomenclature
 If subsituents present, their position should be identified
by the number of the atoms bearing them and then they
should be listed in alphabetical order. Br
4
3

2
5 N
1
H2N O

5-Amino-4-bromoisoxazole
 The words dihydro, or trihydro, or tetrahydro are used if two or
three or four atoms are saturated. These words are preceded by
numbers indicate the position of saturated atoms as low as possible
and followed by the corresponding fully unsaturated trivial name.
H
N

1,2-Dihydro-pyridine
Heterocyclic Chemistry
 Trivial names
1) 5-membered heterocycles with one or two heteroatoms

2) 6-membered heterocycles with one or two heteroatoms

Common azines-six-membered aromatic nitorgrn heterocycles

N
N
N
O O N N N N

2H-Pyran 4H-Pyran Pyridine Pyridazine Pyrimidine Pyrazine

These are tautomers DNA/RNA bases
Both are not aromatic

Heterocyclic Chemistry
 Trivial Names
3) Fused heterocycles

O
N
NH

N N NH2
Guanine

Heterocyclic Chemistry
Trivial Names

O O

O O
O O
Ph
Coumarine Chromen-4-one Flavone
Chromen-2-one

8 9 1
5
6 4
7 2
3
7
6 10 3
2
N
8 9 5 4
N
1
H
H
9,10-Dihydro-acridine
9H-Carbazole

Heterocyclic Chemistry
 Trivial Names
4) Saturated heterocycles

Exercise :

Give the common name of the following compounds:

N H
O N

NH
H2N N CH3

Heterocyclic Chemistry
 II-Replacement nomenclature
 In replacement nomenclature, the heterocycle’s name is
composed of the corresponding carbocycle’s name and an
elemental prefix for the heteroatom introduced (if more than one
heteroatom is present they should be listed according to the
priority order shown in (table 1). According to this nomenclature,
tetrahydrofuran, for instance, is called oxacyclopentane.

Table 1

Atom Prefix

O oxa Priority decreases

Se selena

S thia
N aza
P phospha

Heterocyclic Chemistry
II-
II-Replacement
Replacementnomenclature
nomenclature
N
Benzene 1,4-Diazabenzene
N

Cyclopentadiene Oxacyclopenta-2,4-diene
O

N
Cyclopentadiene 1-Oxa-3-azacyclopenta-2,4-diene
O
Cyclopropane Oxacyclopropane
O
Cyclopropene N
Oxazacyclopropene
O

Cyclopentadiene 1-Thia-2-azacyclopenta-2,4-diene
N
S

O
Cyclohexane 1-Oxa-4-azacyclohexane
N
H

Naphthalene 2-Azanaphthalene
N

Heterocyclic Chemistry
 II- Replacement nomenclature

cyclohexane Thiacyclohexane
S

8 1 1
8a 2
7 2
naphthalene 4H-4a-azanaphthalene
6 4a
3 N 3
5 4 4a 4

S
naphthalene 1,4-dithianaphthalene
S

2 1
N O
cyclododecadiene 1,7-Dioxa-2,8-diazacyclododeca-2,8-diene
O N
7 8

Heterocyclic Chemistry
 III-Hantzsch-Widman nomenclature (IUPAC)

 Hantzsch-Widman nomenclature is named after the

German chemists Arthur Hantzsch and Oskar Widman,
who proposed similar methods for the systematic naming
of heterocyclic compounds in 1887 and 1888 respectively.

 According to this system three to ten-membered rings are

named by combining the appropriate prefix (or prefixes)
that denotes the type and position of the heteroatom
present in the ring with suffix that determines both the
ring size (depending on the total number of atoms in the
ring) and the degree of unsaturation (note that fully
saturated and fully unsaturated have certain rules for
nomenclature while partially unsaturation will be indicated
in certain ways). In addition, the suffixes distinguish
between nitrogen-containing heterocycles and
heterocycles that do not contain nitrogen

 IUPAC name = locants +Prefix + suffix

Heterocyclic Chemistry
 Hantzsch-Widman rules for fully saturated and
fully unsaturated heterocycles

1) Identify the hetroatom present in the ring and choose from

(table 1 on slide 9) the corresponding prefix (e.g. thia for
sulfur, aza for nitrogen and oxa for oxygen).

2) The position of a single heteroatom control the numbering in a

monocyclic compound. The heteroatom is always assigned
position 1 and if substituents present are then counted around
the ring in a manner so as to take the lowest possible numbers.

For example:

4
N1

2
3

CH3

Heterocyclic Chemistry
 Hantzsch-Widman rules
3) A multiplicative prefix (di, tri, ect.) and locants are used
when two or more similar heteroatoms contained in the
ring( two nitrogen indicated by diaza) and the
numbering preferably commenced at a saturated rather
than an unsaturated atom, as depicted in the following
4
N3 example: 1,3-diaza….
5 2
1
N
H
4) If more than one type of hetroatoms present in the ring the name will include more
than one prefix with locants to indicate the relative position of the heteroatoms.

 Atom prefixes have a strict order of priority (preference) in which

they are to be listed. For example,‘’Oxa’’(for oxygen) always
comes before ‘’aza’’ (for nitrogen) in a name (see table 1).

 When combining the prefixes (e.g. oxa and aza) two

vowels may end up together, therefore the vowel on the
end of the first part should be omitted (oxaza).
Heterocyclic Chemistry
 Hantzsch-Widman rules

 The numbering is started from the heteroatom of the

highest priority in such a way so as to give the smallest
possible numbers to the other heteroatoms in the ring
(the substituents are irrelevant). For example the prefix
corresponding to the following compound is 4-Methyl-1,3-
Thiaza…. 4
N3

5 2
1
S

5) Choose the appropriate suffix from (table 2) depending

on whether or not nitrogen atom is present in the ring,
the size of the ring and presence or absence of any
double bonds

6) Combine the prefix(s) and suffix together and drop the

first vowel if two vowels came together.
Heterocyclic Chemistry
 Hantzsch-Widman rules
Table 2

Ring size N-present N-absent

Unsat sat Unsat sat

irine iridine irene irane

ete etane
ete etidine

ole olidine ole olane

ine a in ane

epine a
epin epane

ocine a
ocin ocane
a
9 onine onin onane

10 ecine a
ecin ecane

a: means use the prefix perhydro followed by the fully

Heterocyclic Chemistry
 Hantzsch-Widman rules
 Examples
H
N

• This ring contains (N) Prefix is aza

• The ring is 3-membered and fully saturated
suffix is iridine
• By combining the prefix and suffix, two vowels
ended up together (azairidine), therefore the vowel
on the end of the first part should be dropped. This
gives the correct name: Aziridine

Heterocyclic Chemistry
 Hantzsch-Widman rules
HN O

• This ring contains (O ,N) and (o) has higher

priority than (N) and by starting numbering the
ring at (O) Prefix is 1,2-Oxaaza, but the
first vowel must be omitted to give
1,2-Oxaza
• The ring is 4-membered and fully saturated
suffix is etidine
• By combining the prefix and suffix, two vowels
ended up together (1,2-oaxazaetidine), therefore
the vowel on the end of the first part should be
dropped. This gives the correct name:
1,2-oxazetidine Heterocyclic Chemistry
 Hantzsch-Widman rules
4 3

5 N N2
O
1

 This ring contains (O) prfix1 (oxa), and two (N)

prfix2 diaza
 Locants, since (O) is higher priority than (N) so it is in position 1
by default and the two (N) are therefore at positions 2 and 5,
this gives the combined prefixes as 1,2,5-oxadiaza (note that the
a in oxa is not dropped)
 It is 5-membered,fully unsaturated ring with (N)
the suffix is ole
 By combining the prefixes and the suffix and dropping the
appropriate vowels we get the correct name as
1,2,5-Oxadiazole

Heterocyclic Chemistry
 Hantzsch-Widman rules

N
H

The ring is 6-memberd, fully saturated with N

Prefix perhydro followed by the name of fully unsaturated 6-
memberd ring with nitrogen azine

Thus the full name is perhydroazine

Heterocyclic Chemistry
 Hantzsch-Widman rules
 Exercise:
Explain how can you name the following heterocycles.

Br
N
O

O S N N N S

Heterocyclic Chemistry
 Hantzsch-Widman rules for partially
unsaturated heterocycles
 Partial unsaturation in heterocyclic compounds can
be indicated by one of the following methods:
a) The position of nitrogen or carbon atoms which bear extra
hydrogen atoms must be indicated by numbers and italic
capital H (e.g. 1H, 2H, etc.) followed by the name of
maximally unsaturated ring.

4 3 4
3N 4 5 3
5 2 2S 1 5
O 1 6 1 2
1 N O O
H
2H, 3H-Oxole 1H-Azepine 5H-1,2,3-Oxathiazole 4H-Oxin

Heterocyclic Chemistry
 Hantzsch-Widman rules for partially
unsaturated heterocycles
b) The words dihydro, or trihydro, or tetrahydro are
used if two or three or four atoms are saturated.
These words are preceded by numbers indicate the
position of saturated atoms as low as possible and
followed by the corresponding fully unsaturated
Hantzsch-Widman name.

4 4 4

5 3 5 3 5 3
4 3

6 2 6 2 6 1 2 5
1 1 2
1
N N N
H H O

1,2-Dihydroazine 1,4-Dihydroazine 2,3,4,5-Tetrahydroazine 2,3-Dihydrooxole

Isomers have the same M.F.

but differ in the position of
the double bond

Heterocyclic Chemistry
 Hantzsch-Widman rules for partially
unsaturated heterocycles
c) Alternatively, the partially unsaturated 4 and 5 rings (i.e. rings
contain one double bond) are given special Hantzsch-Widman
suffixes as in table 3 and the double bond is specified as ∆1, ∆2,
∆3, etc.. Which indicates 1 and ; 2 and 3; 3 and 4 atoms
respectively have a double bond
(i.e. Name : ∆x + Prefix + special suffix )
( x= locant of the double bond)

Table 3

Ring size With N Without N

-etine -etene

-oline -olene

Heterocyclic Chemistry
 Hantzsch-Widman rules for partially
unsaturated heterocycles
 Examples

2 4 3 4 3

1 1 1
2 5 2 5 2
HN HN O 1 1
N O
2 2 H
 -Azetine  -Oxetene
3
 -Azoline 2 -Oxolene

3
4
NH 4
N 3

5 2 2
5
1 1
S N
4
H
 -1,3-Thiazoline 2 -1,3-Diazoline

Heterocyclic Chemistry
 Nomenclature of Fused Systems

Definitions:
 Fusion: This term is used to describe the process of joining two
separate rings with the maximum number of non-cumulative
double bonds via two atoms and one common bond.
 Ortho-fused rings: are those rings that have only two common
atoms and one bond, example; naphthalene

Naphthalene

 Ortho-and peri-fused rings: are those found in a polycyclic

compound with a ring that is ortho- fused to different sides
of two other rings that are themselves ortho-fused
together (i.e. there are three common atoms between the
first ring and the other two).
Heterocyclic Chemistry
 Nomenclature of Fused Systems

 For example : 1H-phenalene is considered as being

composed of three benzene rings, each is ortho-peri-
fused to the other two.

1H-Phenalene

 Polycyclic compounds incorporating one heterocyclic ring

or fused heterocylic system fused to benzene are known
benzoheterocycles.
 Also bicyclic compounds with two fused heterocyclic rings
are well known.
Both types can be named according to certain rules
Heterocyclic Chemistry
 I-Nomenclature of Fused Heterocyles

A. Nomenclature of benzofused compounds:

• Unless listed as a trivially named heterobicycle (see slide

6), a benzene ring fused to a heteromonocycle of five or
more members or a heterobicylcle is named by prefixing
the word benzo to a letter indicating the position of fusion
in square brackets by the name of heterocyclic ring
(common or IUPAC or modified replacement name).
Name= Benzo[letter]name of heterocyclic ring
• For designating the position of fusion, the peripheral
bonds of the heterocyclic ring are consecutively assigned
alphabetical letters staring with the 1,2-bond as a side
and the labeling is continued around the ring to give the
common bond the lowest order.

Heterocyclic Chemistry
 I-Nomenclature of Fused Heterocyles

 Examples
1
3
2 a O c b 2 4
4 3
a
b 5
S
1 b 5
d a 1
3 2
4 5 N
7 H
Benzo[b]furan 6

Benzo[d]thiepine Benzo[b]pyrrole
Indole

b f 5
e
4
d c b 2
2
a 1 6
4a
3
3
a
1
N b c S
7
1
a 2
8a 4
Benzo[b]pyidine 8
N 5

Qunioline
Benzo[f]qunioline Benzo[c]thiophene

Heterocyclic Chemistry
 I-Nomenclature of Fused Heterocyles
B. Nomenclature of fused heterocylic compounds:
 Naming a fused heterocyclic systems composed of two
monoheterocyclic units or benzoheterocycles (e.g. chromene)
fused with anotehr hetrocycle ring is based upon considering
one system as the parent (base) and the second is considered
as subsitituent

 The name is formed of :

name of minor ring [number, number-letter] name of major ring

 The name of the minor ring is derived by writing a contracted

prefix for the substituent ring present
Furo from Furan
Imidazo from Imidazole
pyrido from Pyridine
Pyrimido from Pyrimidine
Thieno from Thiophene
Pyridazino from pyridazine
Pyrazino from pyrazine
Chromeno from chromene

Heterocyclic Chemistry
 I-Nomenclature of Fused Heterocyles

 The numbers indicate which atoms in the minor ring are

common to the major ring (fusion sites in minor ring).
 The order of the numbers indicates which atom of the
minor ring is encountered closest to atom 1 in the major
numbering system (i.e. these numbers may be written in
ascending or descending order e.g.2,3 or 3,2 )
 The letter defines the position of attachment of the minor
ring to the major ring (fusion sites in base component)
 Finally a suffix indicate the name of the base ring is
written.
 The numbering system for the whole fused system is not
the same as the numbers in the square brackets (i.e. there
are three numbering systems; one for minor ring, one for
major ring and the third is for the system as a whole)

Priority order of component ring systems:

 Selection of a parent component or attached component is based
on the following rules which are applied in order

Heterocyclic Chemistry
 I-Nomenclature of Fused Heterocyles
Rule 1: A heterocyclic ring containing the heteroatom occuring
earlist in the order N, F, Cl. Br, I, O, S, Se,..
(i.e. ring containing N preferred to the rings does not contain N
or containing O, or S)

5
3 4
1
c N
2 3 a
1
O b 2
Substituent ring Base or parent ring
Chromeno because it has N
pyrrole

Chromeno[2,3-c]pyrrole
Heterocyclic Chemistry
I-Nomenclature of Fused Heterocyles
1
O 7

2 6

3
5
S
4

1 4
a 3
O
2
b 2
3 1
S

Parent ring Substituent ring

O preferred to S Thiopyrano with one satrated C that take locant 7 when
Furan the system is numbered as a whole (starting from O to
give the two heteroatoms locants 1,4 while starting from
S gives them locants 1,5)

7H-Thiopyrano[3,2-b]furan

Heterocyclic Chemistry
 I-Nomenclature of Fused Heterocyles

Rule 2: A heterocyclic component containing the

largest possible individual ring

O Indicated H
1
2
b
3
a
O

2H-Furo[3,2-b]pyran
(pyran [6] preferred to furan [5])

Numbering the whole system is started from O in furan

ring to give the two heteroatoms locants 1,4 while
starting from O in pyran ring gives them locants 1,5, thus
the indicated H takes locant 2

Heterocyclic Chemistry
 I-Nomenclature of Fused Heterocyles
Rule 3: A heterocyclic component containing the
greater number of hetroatoms of any kind
1
8
N
8a
1
b c
7N 2
2
a d
3
6 O 3
4a
5 4

5H-Pyrido[2,3-d][1,2]oxazine
(Oxazine preferred to pyridine)

N.B. The whole molecule is numbered starting from pyridine ring to

give the three heteratoms the lowest locants (1,6,7), however,
stating from oxazine ring will give them locants (2,3,5) or (2,3,8).

Heterocyclic Chemistry
 NOMENCLATURE OF FUSED HETEROCYCLES
Rule 4: A heterocyclic component containing the greater variety of hetroatoms

N.B. The whole molecule is numbered starting from pyrazole ring to give the four heteratoms the lowest locants (1,2,4,6). While starting from oxazole ring give
them locants (1,3,4,5) or (1,3,5,6).
O NH
a 2
3
b d 1N
c 4
5
N

1H-Pyrazolo[4,3-d]oxazole
(O & N preferred to N only)

Heterocyclic Chemistry
 NOMENCLATURE OF FUSED HETEROCYCLES
Rule 5: A heterocyclic component containing
the greater number of heteroatoms most
preferred when considered in order F, Cl, Br,
I, O, S, Se, Te, N, P, As, Sb, Bi, Si, Ge, Sn
Pb, B, Hg
S
1
N c 5 2

b d 4 3
a N
O

[1,3]Thiazolo[5,4-d][1,3]oxazole
(N & O preferred to N & S)

Heterocyclic Chemistry
 NOMENCLATURE OF FUSED HETEROCYCLES
Rule 6: A heterocyclic component with the lower
locants for heteroatoms
b c N
N 1
2
a d
3
N
N
Pyrazino[2,3-d]pyridazine
(pyridazine [2N-1,2] preferred to pyrazine [2N-1,4]

Exercise: Name the following compound.

O

S
N
H
Heterocyclic Chemistry
 NOMENCLATURE OF FUSED HETEROCYCLES
Rule 7: If a position of fusion is occupied by a heteroatom the
name of the component rings to be used are so chosen as both
to contain the heteroatom.

S
N a
3 2 b
1
N

Imidazo[2,1-b]thiazole

Heterocyclic Chemistry
 Order of preference between alternative
numbering system of the whole molecule
 Numbering the whole fused system should start from the
first atom after fusion in any direction to fulfill the following
rules in order:
a) Give low numbers for the heteroatoms as a set
H
6 N1 4 H3 H 4
N 3 N
5 2 2 5
N 5 2
O 3 N N
4 O 1 O 6
6 1
1H-Furo[2,3-d]imidazole
(heteroatoms 1,3,4 is preferred to 1,3,6 or 1,4,6)

b) Give low numbers for heteroatoms of higher priority i.e. O,S,

N
6 1
S O
5 2

4 3
4,5-Dihydro-thieno[2,3-b]furan Heterocyclic Chemistry
 Order of preference between alternative
numbering system of the whole molecule
c) Give low numbers to fusion carbon atoms

1 4 5
7 N 6 N 3 4 N
8 5 6
N 2 N 3 N

6 Not 7 Not 2
3 2 7
N N 8a N 8a N
4a N N 1
5 4 8 8
1
Imidazo[1,2-b][1,2,4]triazine
fusion C -4a is preferred to 8a

d) Give low numbers to indicated hydrogen atom

6 1 4
N 3
O N O

2
5

Not
 
5
2
4N O N
H O
3 H
1
6
2H,4H-[1,3]dioxol[4,5-d]imidazole
Indicated hydrogens 2,4 not 2,6
Heterocyclic Chemistry
 NOMENCLATURE OF HETEROCYCLES
 Exercise
Q1. Name the following compounds (a-d):

N
S H
N O
S
N
N N
N N

(a) (b) (c) (d)

Heterocyclic Chemistry
 Summary of Nomenclatures Rules

Scheme for deriving the base component of' a fused ring system
1. Is there only one ring which contains nitrogen?
(YES:. choose this as base component)
2. Are the two rings have the same heteroatoms but their size is
different ?
(Yes: choose the larger one )
3. Are the two rings of the same size but have different
heteroatoms?
(YES: choose the ring containing a heteroatom of the highest
priority i.e. O >S)
4. Are the rings of the same size but contain different numbers of
heteroatoms?
(Yes: choose the ring with the greater number )
5. Are the two rings of the same size and the same number of
different heteroatoms?
(Yes: choose the ring with the greatest variety of heteroatoms
7-Are the two rings have the same size and the same number and
type of heteroatoms?
(yes: choose the ring with the lower numbers for heteroatoms )

Heterocyclic Chemistry