About the Authors

Mohamed Hilmy Elnagdi was born in Egypt 1941. He graduated in 1962

(Cairo University) where he also worked and obtained his M.Sc. (1966) and
Ph.D. (1969) Diploma in Applied Chemistry (Japan), 1973 and D.Sc. (1982).
Degrees. He was awarded The Alexander von Humboldt Fellowship at
University of Bonn with Prof. H. Wamhoff and has several sabbatical leaves
with plenty of German scientists. He also received fellowships from several
institutions in Norway, USA and Japan. He worked at Cairo University as
Professor of Organic Chemistry since 1980 and as visiting Professor to
Kuwait University 1993-1999 and from 2003 till now. Prof. Elnagdi has
specialized in the synthesis of polyfunctional heterocycles and has several
national and regional research awards.
Kamal Usef Sadek was born in El-Minia (Egypt) and has received B.Sc.
degree (honors) in applied chemistry from Assiut University (Egypt) in
1969. He obtained his M.Sc. and Ph.D. from Cairo University. He was
appointed as demonstrator in Minia University (1970). Since then he was
appointed as Lecturer (1980), Associate Professor (1985) and full Professor
(1990). In 1987 he was awarded the Alexander von Humboldt Foundation
fellowship with Prof. W. weigrebe in Regenesburg University and has
several study leaves with Prof. M.Regitz of Kiserslautern University and
Prof. H.H. Otto of Frieburg University. Currently, he is working in
developing green technologies for the synthesis of biologically active
heterocycles.
Dr. Moustafa Sherief Moustafa was born in Egypt on July 13th 1981. He
graduated from the Faculty of Science at Cairo University in May 2002 and
in February 2012 obtained his Master degree from Kuwait University which
received the University of Kuwait Prize for the best Master thesis in the
academic year 2011-2012. Since 2005 Mr. Moustafa is working as research
assistant in the chemistry department University of Kuwait, during his
period he published two books, three reviews and 25 research papers till
2014.
Dr. Saleh Mohammed Al-Mousawi was born in Kuwait on November 1st 1953. He graduated from the Faculty of Science at Kuwait University in
1975 and in 1980 obtained his Ph.D. from Bristol University U.K. on
synthetic organic chemistry. Dr. Al-Mousawi Prof. Elnagdi did work all the
time in Kuwait University. He started as assistant professor in the period of
1980-2005 then associate professor till now. Dr. Al-Mousawi published 38
papers in the field of organic chemistry till 2014.

Copyright Prof Dr Mohamed Hilmy Elnagdi, Prof Dr Kamal Usef

Sadek, Moustafa Sherief Moustafa, Dr Saleh Mohammed Al-Mousawi
(2015)
The right of Prof Dr Mohamed Hilmy Elnagdi, Prof Dr Kamal Usef
Sadek, Moustafa Sherief Moustafa, Dr Saleh Mohammed Al-Mousawi
to be identified as authors of this work has been asserted by them in
accordance with section 77 and 78 of the Copyright, Designs and
Patents Act 1988.
All rights reserved. No part of this publication may be reproduced,
stored in a retrieval system, or transmitted in any form or by any
means, electronic, mechanical, photocopying, recording, or otherwise,
without the prior permission of the publishers.
Any person who commits any unauthorized act in relation to this
publication may be liable to criminal prosecution and civil claims for
damages.
A CIP catalogue record for this title is available from the British
Library.

ISBN 978 1 84963 991 4

www.austinmacauley.com
First Published (2015)
Austin Macauley Publishers Ltd.
25 Canada Square
Canary Wharf
London
E14 5LB

Printed and bound in Great Britain

Contents

Introduction

11

Chapter 1 Nomenclature of Heterocycles

12
12

1. Introduction

Chapter 2 Aromaticity of fully Unsaturated Heterocycles and its Reflect on The

Chemical Reactivity
21
2.1. Introduction

21

2.2. Aromatic Monoheteroaromatic Fully Unsaturated Heterocycles

21

2.2.1 The Pi-excessive Molecules

22

2.2.2 Pi-deficient Molecules

22

2.2.3. The Azoles

23

2.4. Other Aromatic Systems

24

2.4.1. Monocycles

24

2.4.2. Polycycles

25

2.5. Ring Current

26

2.6. Resonance Energy Stabilization

28

Chapter 3 Chemical Reactivity of Aromatic Heterocycles

29

3. General Consideration

29

3.1. Electrophilic Substitution

29

3.2. Typical Reactivity Pattern of Aromatic Heterocycles with Electrophiles

34

3.2.1. Halogenation

34

3.2.2. Nitration

37

3.2.3. Alkylation; Acylation; Mannich like and Michael Addition like Reactions 40
3.2.3.1 Alkylation

40

3.2.3.2. Acylation

50

3.2.4 Coupling with Aromatic Diazonium Salts

52

3.3. Reactivity of Heteroaromatics Towards Nucleophilic Reagents

53

3.4. Amination (The Chichibabin Aminatian)

59

3.5. Photochemistry of Heterocyclic Compounds

63

3.6. Thermal Cycloaddition and Precyclic Reactions

73

Chapter 4 Functional Group Reactivity

87

4.1. Alkyl, Alkenyl Functions

87

4.1.1. Reactivity of -deficient Heterocycles

87

4.1.2. Reactivity of -excessive Heterocycles

93

4.2. Reactions with Nucleophilic Reagents

101

4.3. Oxygen Containing Functional Groups

102

4.4. Heteroaromatics Amines

107

Chapter 5 Synthesis of Heterocycles

115

5. Heteroaromatics

115

5.1. Introduction

115

5.1.1. Intramolecular Condensation

115

5.1.2. Addition, Condensation and Condensation Addition Routes

142

5.1.3. Synthesis of Heterocycles via Pericyclic Reactions

148

5.1.3.1 Cycloadditions

148

5.1.3.2. Electrocyclic Reaction

149

5.1.3.3. Sigmatropic Rearrangements

150

5.1.3.4 Cheletropic Reactions

150

5.1.4. Rules for Electrocyclic Reactions

154

5.1.5. Dipolar Additions

156

5.1.6. Reactions Leading to Interesting Heteroaromatics are

157

5.1.6.2. [2+2] Cycloaddition

160

5.1.6.3. Cheleotropic Reactions

161

Chapter 6 Functionally Substituted Arylhydrazones as Precursors to Five and

Six Membered Heterocycles
163
6.1 Introduction

163

6.2 Arylhydrazones as 3 and 4 Atom Precourser to Nitrogen Heterocycles

163

6.3. Arylidenemalononitrile as Precursors to Heterocycles

166

6.4 Functionally Substituted Enamines as Versatile Reagents for Synthesis of

Polyfuntionally Substituted Heteroaromatics
167
6.5. Utility of Enaminones as Precursors to Heterocycles

169

6.6 Oxoalkano Nitriles as Precursors to Heterocycles

171

Chapter 7 Heterocycles and Life

172

7.1. Heterocycles and Life

172

7.1.1 Role of Carbohydrates in Life.

173

7.2. Steroelectronic Effects.

174

7.2.1. Carbohydrate Metabolism

175

7.3. Biosynthesis of Oxygen Heterocycles

179

7.4. Synthesis of Natural Heterocycles from Cinnamic Acid

182

7.5. Basic Chemistry behind this Synthesis and how Nature Affect That

183

7.5.1. Biosynthesis of proline

186

7.5.2. Syntheses of Adenine and Guanine197

186

7.5.3. Pyrimidine Synthesis

189

Chapter 8 Heterocycles as Dyes and Pigments

191

8.1. Introduction

191

8.2. Synthetic Heterocyclic Dyes

192

8.2.1. Azodyes

192

8.3. Heterocycles as Organic Pigments

205

8.3.1. Introduction

205

8.4. Heterocycles in High Technology Applications

207

8.4.1. Photochromic Heterocycles

207

8.4.1.1. Diheteroaryl Ethylenes

208

8.4.2. Electrocyclic Reactions of Fulgides

212

8.4.3. Spirooxazines

213

8.4.4. D2T2 Printing

214

8.4.4.1. Properties required of D2T2 Dyes

215

Chapter 9 Heterocycles as Drugs

216
216

9.1. Introduction
Chapter 10 Heterocycles as Explosives

227

10.1. Introduction

227

10.2. Pyrazoles Hide and Seek

228

10.3. 1, 3,4 Oxadiazoles

229

Chapter 11 Heterocyclization during Food Cooking

233

11.1. Caramelisation

233

11.2. Millard Reaction3

233

Chapter 12 Heterocycles as Organic Metals

238

Chapter 13 Green Synthesis of Heterocycles

241

13.1. Introduction

241

13.2. Green Chemistry Principles

241

13.3. Green Synthesis

242

13.4. Catalysts

242

13.5. Solvents

242

13.6. Multicomponent One-pot Syntheses

242

13.7. Utility of Renewable Energy Sources and Feed Stocks

242

13.8. Synthesis of Pyrans and Thiopyrans

243

13.9. Synthesis of pyridines

244

13.10. Synthesis of Pyrazolo [1, 5-a] Pyrimidines

247

Introduction
This book is based on courses we designed while teaching heterocyclic
chemistry courses in Egyptian Universities, in Libya and in Kuwait as well
as in Saudi Arabia for almost fifty years. Needless to say, that the course
material has changed several turns until we arrived at this framework.
Unfortunately all textbooks of organic chemistry and texts of chemistry
devoted to chemistry of heterocycles, with only perhaps one recent book,
describes the chemistry of only synthesized heterocycles but ignores dealing
with those made by nature, although no doubt that life only started when
algae could photosynthesise carbohydrates and the majority of these are
derivatives of either pyran or furan. r furan. In this text we will start with
chemistry of aromatic heterocycles and their nomenclature. Also a chapters
that demonstrating the existing role of heterocycles in chemical industry
basically as dye ingredients, pharmaceuticals, agrochemicals, and catalyses
as well as other less familiar purposes are cited. Then shifted to heterocycles
manufactured by nature showing how nature since life beginning managed to
synthesis heterocycles in nature simple way swiftly and at ambient
temperature. By the end the brief chapter demonstrating green synthesis of
heterocycles will be described. We hope that we will be able to come to a
modern text that encourages chemistry in structures as well as researchers to
go back to this vital field.

Prof. Dr. Mohamed Hilmy Elnagdi

Prof.Dr. Kamal Usef Sadek
Moustafa Sherief Moustafa
Saleh Mohammed Al-Mousawi

Chapter 1
Nomenclature of Heterocycles

1. Introduction
At the early days of heterocyclic chemistry no one predicted the potentiality of
this science and heterocycles at these days were given names indicating origin
like caffeine (1) extracted from coffee or and pyrrole (discovered in 1857) from
pyrolysate of bone and the name was derived from the Greek word that means
red referring to its color.
H3C

N
N

N
N

CH3
O

N
H

CH3
1
Caffeine

2
Pyrrole

After a short period the need for systematic nomenclature become apparent
and Hanzsch1 and Widman2 have independently suggested the nomenclature
system that carry their names. The IUPAC nomenclature still approves this
method and the trivial names for ring systems shown in chart 1 were also
approved.3

A. Hantzsch and J.H. Weber, Ber. Dtsch. Ges. 20 , 3228 (1887).

O. Widman, J. Prakt. Chem. 38 , 185 (1888).
3
IUPAC Nomenclature of Organic Chemistry, Definitive Rules, Sections A to H, Pergamon
Press, Oxford, 1979.
2

Thiophene

Furan

Te

Se

Tellurophene

Selenophene

N
N

N
H
1H-imidazole

N
H
Pyrrole

Isoxazole

Furazane

N
N

Pyridazine

Pyrazine

N
N
H
Pyrazole

O
4H-pyrane

N
N

N
N

N
H

Pyridine

Isothiazole

Purine

N
Pyrimidine
N

NH
N
H

N
H

S
2H-Thiopyrane Indole

1H-Indazole

Isoindole

N
Phthalazine

Quinoline
H
N

Cinnoline
H
N

N
Quinazoline

N
H
Piperidine

N
H
Piprazine

O
Morpholine
N

O
Chromene

N
Pteridine

Isoquinoline

N
N

N
H
Pyrrolindine

1.1. The Hanzsch and Widman Nomenclature

The rules used are:
1- The name of the ring is derived by placing a prefix to indicate the
heteroatom or heteroatoms in the ring and a suffix that indicates the ring
size. In the table 1 and 2 are listed the approved prefixes and suffixes4.
Examples:
O
O
Oxol

O
Oxolane

N
H
Azolidine

Oxiran

O
Oxirine

Table 1: Prefixes for noncarbon elements

Element
Flour (F)
Chlore (CI)
Bromine (BR)
Iodine (I)
Oxygen (O)
Sulphur (S)
Selenium (Se)
Tellurium (Te)
Nitrogen (N)
Phosphorous
(P)
Arsenic (As)
Antimony (Sb)
Bismuth (Bi)
Silicon (Si)
Germoium (Ge)
Tin (Sn)
Lead (Pb)
Boron (B)
Mercury (Hg)

Valence
1
1
1
1
2
2
2
3
3
3

Prefix
Flour
Chlora
Broma
Ioda
Oxa
Thia
Selena
Tellura
Aza
Phospha

3
3
3
4
4
4
4
3
2

Arsa
Stilba
Bisma
Sila
Germa
Stanna
Plumba
Bora
Mercura

IUPAC Commission on Nomenclature of Organic Chemistry, Pure & Appl. Chem. 55, 409
(1983).

2. If the ring contains more than one heteroatom of the same type the term
di, tri. and tetra. etc... is used to indicate the number of these atoms and
allocate number is used to indicate their place in the ring. The
heteroatom that would give next heteroatom and/or substituent least
number is given number l. Example:

HO2C

5
1

N
H

3
2

1,3-Diazole-4-carboxylic acid

Table 2: Systems for Hantzsch-Widman names

Ring
Size
3
4
5
6*
7
8
9
10

Rings Containing Nitrogen

Unsaturated
Irine
Ete
Ole
Ine
Epine
Ocine
Onine
Ecine

Saturated
Iridine
Eidine
Olidine
Ane**
****
****
****
****

Rings Containing No Nitrogen

Unsaturated
Irene
Ete
Ole
Ine
Epine
Ocine
Onine
Ecine

Saturated
Irane
Etane
Olane
Inane***
Epane
Ocane
Onane
Ecane

* suffixes irine and irane are used for rings in which the last named element
is F, Cl, I, O, As, or Sb.
** For rings in which the last named element is O, S, Se, Te, Bi, or Hg.
*** For rings in which the last named element is N, Si, Sn, Pb or B
**** Expressed by prefixing perhydro before name of unsaturated.
3. If two or more different heteroatoms are present, the one in higher place
in table 2 is indicated firstly and counting ring corners should start from
this atom then goes in the direction that gives the next atom the least
possible number. Example:

4
3

Cl
O1

5-Chloro-1,3-oxazole

4. if trivial names are used for naming rings having sp3 atom, H location
should be used to indicate this atom.

N
H
1H-Pyrrole

N
H

4H-Pyrazole

1H-Indole

5. If the heterocyclic ring has an alkyl and halide substituent in case of

existence of a choice, counting should go in the direction that gives the
least number for either. Example:-

H3 C
N
H

Cl

2-Chloro-4-methyl-1H-pyrrole

6. If the hetero rings carry a substituent other than alkyl and halide, the
ring is considered as a derivative of this function. Examples:-

H2N

CO2H
N

NH

1H-Pyrrole-4-amine

Isoxazole-3-carboxylic acid

7. If the heterocyclic ring is carrying more than one substituent the

substituent of highest priority is taken as the parent. Example:-

H2N

CO2Et
S

Ethyl 4-aminoisoxazole-3-carboxylate

1.2. IUPAC Nomenclature

According to the IUPAC rules, an organic compound must be allocated to the
first appropriate class of compounds in the following list to which it belongs.
The classes are arranged in order of decreasing priority:

a. Cation and anions

b. Acids: carboxylic,
c.
d.
e.
f.
g.
h.
i.
j.
k.

peroxycarboxylic, thiocarboxylic, sulfonic,

Sulfinic,...etc
Derivatives of acids: anhydrides, esters, acyl halides, amides,
hydrazides, imides, amidines, ...etc.
Nitriles: (cyanides), isocyanides.
Aldehydes, thioaldehydes and their derivatives.
Ketones, thioketones and their derivatives.
Alcohols, phenols, thioles and their ester derivatives with inorganic
acids
Hydroperoxides.
Amines, imines and hydrazines
Ethers, thioethers.
Peroxides

All other functional groups which are included in one of these classes are
then written as prefixes in the form of the name in alphabetic order.
Fusion names
1- The monocyclic components of fused systems are firstly defined.
Approved trivial names should be used, and if not available the
Hantzsch-Widman names should be used.

b
d

f
e

c
4

2
a

N
1

N
f

HN
1

4
5

Pyrrolo[1,2-a]pyrimidine

2. The larger ring is chosen as parent so long as it contained nitrogen,

if not choose the ring having a heteroatom which ranks highest in
Table 2.
3. The name of the daughter ring is written first and the ending (e) is
replaced by parent ring (or some rings are further abbreviated (cf.
list). Brackets [ ] are placed between the daughter ring name and
parent one.
c

b
d

a
e

Pyrrolo[1,2-a]pyrimidine

Some prefixes are further appreciated, as exemplified in the following list

Acenaphthylene
Anthracene
Benzene
Furan
Imidazole
Isoquinoline
Naphthalene
Perylene
Pyridine
Pyrimidine
Quinoline
Thiophene

Acenaphtho
Anthra
Benzo
Furo
Imidazo
Isoquino
Naptho
Perylo
Pyrido
Pyrimido
Quino
Thieno

4. The corners of the daughter ring are given as numbers while that of
the parent are indicated by letters.

5. The position of a junction is now defined by citing between

brackets the numbers of the smaller ring then letters of the parent
ring. The number met firstly while counting the parent is written
firstly.
N

N
N

NH

N
H

N
Pyrazolo[5,1-c]triazine

1H-Pyrazolo[4,5-d]pyrimidine

2H-Pyrazolo[3,4-d]pyrimidine

6. Counting the ring as a whole should start from a position adjacent

to the ring junction. The best way to do this is to place, as many
rings as possible in one line and extract rings should be placed up
on the right hand and in a way that enables giving the least possible
numbers to heteroatoms when counting starts from the most
anticlockwise position and continues clockwise.
1
N

2
N 3

N
H 5

5H-Pyrimido[5,4-b]indole

7. If fusion has occurred between two five membered rings containing

nitrogen, the one with heteroatom of highest priority is considered
parent.
O
N
N
Imidazo[2,1-b]oxazole

N
N

Pyrano[2,3-c]pyrazole

8. If both ring components contained the same atoms, the ring with
least separation between heteroatoms is considered parent.56

A.D. McNaught and P.A.S. Smith, Comprehensive Heterocyclic Chemistry, A.R. Katritzky
and C.W. Rees Ed. Academic Press, New York, 1, 7 (1948).

H
N
N
N
1H-Imidazo[1,2-b]pyrazole
and not
Pyrazolo[3,2-b]imidazole

IUPAC Commission on Nomenclature of Organic Chemistry Nomenclature of Fused and

Bridget Fused Ring Systems, Pure & Appl. Chem., 70, 143 (1998)

Chapter 2
Aromaticity of fully Unsaturated
Heterocycles and its Reflect on The
Chemical Reactivity
2.1. Introduction
The term "Aromatic" was initially made to distinguish a group of coal tar
distillation products that has certain "Aromatic" oder. When it is said that a
compound is aromatic in character it is generally meant that this compound
although having multiple bonds it prefers to react by substitution rather than by
addition to keep its aromatic identity. This preference is a result of stabilization
that is inferred upon the aromatic system as a result of the existence of a
conjugated double bond system. Molecular orbital (M.O) theories predict extra
stabilization for a system that can be presented in more than one ground state
electronic distribution by moving in one plain, electrons form one part of the
molecule to the other part. According to Hckels systems with the number of its
-electron equals (4n + 2) in one cycle are aromatic in character and have extra
stabilization.7
Typical for aromatic systems is benzene (6 electrons) that can have two
contributing resonance forms (cf. 1).

Fully unsaturated five and six membered rings as well as some larger rings
are aromatic in the sense that they "tend" to react by substitution rather than
addition. This tendency varies from one system to other, as we will see later.
However, aromaticity in heterocycles differs than that in aromatic benzene
derivatives in several aspects. In fact we have several different situations for
cloud distribution that differ than the case of the cloud distribution in benzene
which is regarded as a regular hexagon with uniform distribution of electrons
so as the share of each carbon is unity. If we considered this situation as base
then for heterocycles we have the following cases.

2.2. Aromatic Monoheteroaromatic Fully Unsaturated

Heterocycles
7

M.K. Cyranski, T.M. Krygowski, A.R. Katritzky and P. von R. Schleyer, J. Org. Chem., 67,
1333 (2002).

2.2.1 The Pi-excessive Molecules

For these rings to have aromatic stabilization, heteroatom lone pair should
participate to the resonance and as a result of this participation charge separated
forms with -Ve charges residing at carbon corners can result. (cf. scheme 1).

We have a situation of six electrons for five corners and thus some of these
corners should have more than of unit electrons and for this reason these
molecules are called pi-excessive molecules. This ground state electronic
distribution. M.O. calculations for furan (2) and pyrrole (3) indicate that the ring
corners are electron rich as compared to those of benzene.8 9 10
1.10

1.07
1.08

1.09

O
1.71

N
H
1.61

2.2.2 Pi-deficient Molecules

While the two resonating forms 4 and 5 are similar to those of benzene, the
heteroatom electronegative element tends to withdraw electrons from ring
carbons and the carbons and to heteroatoms are thus pi-deficient.
In Scheme 2 the resonating forms for pyridine, as typical example are shown.
Results of M.O. calculations of electron density in pyridine and pyrimidines
are also shown (cf, 6 and 7).11 12

For a review see: A.R. Katritzky , Handbook of Heterocyclic Chemistry, Pergamon Press,
Oxford, UK, pages 58, 571, (1985).
9
C.W. Bird, Tetrahedron , 42, 89 (1986).
10
P. von R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao and N.J.R. von Hommes, J. Am.
Chem. Soc. 118, 6317 1996.
11
For a review see: L.I. Belen,kii, V.N. Gramenitskaya, The Literature of Heterocyclic
Chemistry, Part VIII, 1999-2001 Adv. In Heterocyclic Chem, 87, 1, (2004).
12
For a reiew see: L.D. Quin and J.A. Tyrell, Fundamental of Heterocyclic Chemistry, Jown
Wiley & Sons Inc. Chapter 7, 131 (2010).

X
5

X
4

0.932

N
1.166

1.064

0.803

0.866

1.137

N
0.729

N
1.225
7

Scheme 2

2.2.3. The Azoles

The term azole has been developed to refer to five membered heterocycles in
which one or more carbons of the carbon corners of a monoheteroatomic
heterocycles is replaced by nitrogen. There are generally two families 1,2-azoles
(8) and 1,3-azoles (9).
4
3

5
X1
N2

3 N

X1
2

In both systems while atom X donates electrons to the system ring carbon
to the heteroatom in electron rich (C-4 in 8and 9), nitrogen atom with its fixed
lone pair withdraw electrons from carbons and with respect to it. (Scheme 3
and 4). This will also have its reflect on the physical properties and the chemical
reactivity pattern of these molecules.13

13

Z. Chen, C.S. Wannere, C. Combinboeuf, R. Puchta and P. von R. Schleyer, Chem. Rev.,
105, 3842 (2005).

2.4. Other Aromatic Systems

2.4.1. Monocycles
According to Hckel rule any monocyclic system with 4n+2 electrons would
be aromatic. Thus we may go to the extreme that O3 (X = Y = Z=O) & N3 (X =
Y = Z = NH) may be aromatic. However, ozone is acyclic system and also
triazidine is predicted to have open structure. This is due to the fact that in (10)
the lone pairs are not planner.14 In four membered rings only dithiete ring (X =
Y = S) (11) seems to be stable than open chain isomer.15
If we look at larger rings, the nine membered ring 12 and eight membered
ring 13 seems to be aromatic unless R substituent is electron attracting. The aza
annulene 14 is planner and NMR indicates its aromaticity.16 17

18

9
Z

Y
N

R
10

14

11

12

13

14

C. Leuenberger, L. Hoesch and A.S. Dreiding, J. Chem. Soc., Chem. Commun., 1197
(1980).
15
J.D. Goddard, J. of Computational Chemistry, 8, 389 (1987).
16
M. Breuninger, R. Schwesinger, B. GallenKamp, K.-H. Muller, H. Fritz, D. Hunkler and H.
Prinzbach, Chem. Ber. , 131, 3161 (1980).
17
W. Gilb and G. Schroder, Chem. Ber., 115, 240 (1982).

2.4.2. Polycycles
a) Benzofused heterocycles:
Although benzofused heterocycles show bond alternations corresponding to
kekule structures (15-24), like naphthalene they prefer to react by substitution
rather than by addition while other criteria indicate that they can generally be
considered aromatics.

N
N

N
15

16

19

18

17

N
H

N
H

N
N
H
20

O
21

22

23

24

b) Other polycyclic systems:

Large number of 10 electron systems can be drawn by fusion of two
heteroaromatic rings. At least systems (25-28) are planner and behave like
aromatic compounds. Even when ring junction is nitrogen, (29-31) the systems
are still aromatic.