Chemistry of Heterocyclic Compounds: Chemistry of 1,2,3-Triazines and 1,2,4-Triazines, Tetrazines, and Pentazin, Volume 33

1353 Pages·1978·10.9 MB·English

CHEMISTRY OF
I ,2,3- TR IA ZIN E S
AND 1,2,4-TRIAZINES,
TETRAZINES, AND PENTAZINES
This IS the Tlzirry-Third Volume in the Series
THE OF HETEROCYCLIC COMPOUNDS
CHEMISTRY
THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS
A SERIES OF MONOGKAPHS
ARNOLD WEISSBERGER and EDWARD C. TAYLOR
Editors
1,2,3-TRIAZINES A
1,2,4-TRIAZINES
TRAZINES, A
PENTAZINES
Hans Neunhoeffer
TEY2HNISCHE HOCHSCHULE DAKMSTADT
Paul F. Wiley
THE UPJOHN
COMPANY
AN INTERSCIENCE @ PUBLICA’I’ION
JOHN WILEY & . SONS
-
NEWYORK CHICHESTER * BRISBANE * TORONTO
An Interscience 63 Publication
Copyright 0 1978 by John Wiley & Sons, Inc.
All rights reserved. Published simultaneously in Canada.
Reproduction or translation of any part of this work
beyond that permitted by Sections 107 or 108 of the
1976 United States Copyright Act without the permission
of the copyright owner is unlawful.
Library of Congress Cataloging in Publication Data
Neunhoeffer, Hans, 1936-
Chemistry of 1,2,3-triazines and 1,2,4-triazines,
tetrazines, and pentazines.
(The Chemistry of heterocyclic compounds; v. 33)
“An Interscience publication.”
Bibliography: p.
1. Triazines. 2. Tetrazine. 3. Pentazine.
I. Wiley, Paul Fears, 1916- joint author.
11. Title.
QD401.N62 547’.593 77-18932
ISBN 0471-03129-1
To MARGARET
ELLEN and HENRIK
The Chemistry of Heterocyclic Compounds
The chemistry of heterocyclic compounds is one of the most complex branches
of organic chemistry. It is equally interesting for its theoretical implications, for
the diversity of its synthetic procedures, and for the physiological and industrial
significance of heterocyclic compounds.
A field of such importance and intrinsic difficulty should be made as readily
accessible as possible, and the lack of a modern detailed and comprehensive
presentation of heterocyclic chemistry is therefore keenly felt. It is the intention
of the present series to fill this gap by expert presentations of the various
branches of heterocyclic chemistry. The subdivisions have been designed to
cover the field in its entirety by monographs which reflect the importance and
the interrelations of the various compounds, and accommodate the specific
interests of the authors.
In order to continue to make heterocyclic chemistry as readily accessible as
possible new editions are planned for those areas where the respective volumes in
the first edition have become obsolete by overwhelming progress. If, however,
the changes are not too great so that the first editions can be brought up-to-date
by supplementary volumes, supplements to the respective volumes will be
published in the first edition.
ARN0 LD WE IS SB ERG F. R
Research Laboratories
Eastman Kodak Company
Rochester, New York
EDWARDC .TAYLOR
Princeton University
Princeton, New Jersey
vii
Preface
This volume presents, with the exception of the 1,3,5-trial.ines,t he chemistry of
all six-membered nitrogen heterocycles containing more than two nitrogen
atoms in the ring. It also covers all condensed systems containing these rings.
The first volume discussing the chemistry of these ring systems was originally
published in 1956, covering the whole literature through Chemical Abstracts,
1950. The large growth of research in these different areas has led to many new
reactions and the synthesis of formerly unknown systems. Many new and
important pharmaceutical and agricultural chemicals are heterocycles with more
than two nitrogen atoms in a six-membered ring. Therefore it is felt that a new
review of the chemistry of 1,2,3-triazines, 1,2,4-triazines, I ,2,4,5-tetra~ines,
1,2,3,4-tetrazines, 1,2,3,5-tetraaines,a nd pentazines is justified.
This volume attempts to cover all the literature on these heterocyclic systems
from the earliest references through those appearing in Chemical Abstracts in
1974, we have tried to list in the tables all compounds known during this period.
As far as possible every article was consulted in the original, and we are grateful
to all those colleagues who sent us reprints or copies of articles published in
journals not available in our libraries.
For the convenience of practitioners in this area of chemistry and other
users of this volume, the order is maintained as far as possible as in the original.
For each heterocyclic system the aromatic compounds are considered first,
followed by progressive degrees of hydrogenation. After the condensed systems
a chapter discussing the uses and biochemical aspects of the mentioned class was
added. For every group of compounds methods of preparation are described
first, followed by tables containing all known compounds, a discussion of the
physical properties, and finally the chemical properties.
We trust that this volume will prove readable and useful to those engaged in
research or development on the different heterocyclic systems discussed. We also
hope that it will stimulate additional research in the chemistry of triazines,
tetrazines, and pentazines.
We want to thank Mrs. Gilian Peters for her kindness in reading portions of
the manuscript and offering valuable criticisms and suggestions and Mrs. Susan
ix
Preface
X
Bliss for secretarial assistance. We want especially to thank our wives, Margaret
Neunhoeffer and Veronica Wiley, for their assistance in the preparation of the
manuscript.
HANS N ELI N 13 0 E FF ER
Darmstadt, Germany
PAULF . WILEY
Kalamazoo, Michigan
August 1977
Contents
1,2,3-TRIAZINES H. Neunhoeffer 1
I. Introduction 3
11. Uncondensed Aromatic Systems 5
111. Uncondensed Reduced Systems 12
I. Dihydro-l,2,3-triazines 12
11. Hexahydro-1,2,3-triazines 13
IV. 1,2,3-Triazine Rings Condensed with Carbocycles 14
I. Condensed with the Benzene Ring 14
A. 4-Alkyl- and 4-Aryl-Substituted 1,2,3-Benzot riazines 14
B. 1,2,3-Ben/otrIazin4-ones 17
(4-Hydroxy-l,2,3-benzotrIazincs)
C. 1,2,3-Benzotriazin4(2H)-ones, 1,2,3-Benzotriazinium Betaines 62
D.
1,2,3-Benzotriazine-4-thione4s-,M ercapto-1,2,3-benzotriazines,
and Related Betaines 61
E. and
4-Amino-l,2,3-benzotriazines4,- Imino-l,2,3-benzotriazines,
Related Betaines 72
F. 4-(Hydroxylamino)-, 4-Hydrazino-, and 4-Azido-l,2,3-
benzo triazines 80
G. 1,2,3-BenzotriazineN -Oxides 83
H. 90
Dihydro-l,2,3-benzotriazines
11. Condensed with the Naphthalene System 95
A. Naphtho[2,3u'] 1,2,3-triaaines 95
B. Naphtho[l ,We] 1,2,3-triazines 98
111. Condensed with the Acenaphthylene System 110
A. Acenaphtho(5,Bdel 1,2,3-triazines 110
V. 1,2,3-Triazine Rings Condensed with Heterocycles through Carbon
Atoms 1 I5
I. Condensed with the Pyrrole Ring 115
A. Pyrrolo[3,2d] 1,2,3-triazines 115
11. Condensed with the Indole System 115
A. 1,2,3-Triazino[5,6-b] indoles 115
111. Condensed with the Pyrazole Ring 116
A. Pyrazolo[3,44] 1,2,3-triazines 116
B. Pyrazolo[4,3-d] 1,2,3-triazines 117
IV. Condensed with the Imidazole Ring 118
A. Imidazo[4,54] 1,2,3-triazines 118
xi
xii Contents
V. Condensed with the 1,2,3-Triazole Ring 125
A. 1,2,3-Triamlo[4,5-d] 1,2,3-triazines 125
VI. Condensed with the Thiophene Ring 126
A. Thieno[2,311j 1,2,3-triazines 126
B. Thieno[ 3,241 1,2,3-triazincs 127
C. Thieno[3,44]1 ,2,3-triazines 128
VII. Condensed with the Benzo[b ] thiophene System 128
A. Benzothieno [ 2,341 1,2,3-triazines 128
B. Benzothieno[3,211] 1,2,3-triazines 128
VIII. Condensed with the Thieno[2,311] pyrazole System 129
A. Pyrazolo[4',3': 4,5] thieno[3,211] 1,2,3-triazines 129
IX. Condensed with thc Thiazole Ring 129
A. Thiazolo[5,4-d] 1,2,3-triazines 129
X. Condensed with the Pyridine Ring 130
A. Pyrido[2,36]1 ,2,3-triazines 130
B. Pyrido[3,211] 1,2,3-triazines 130
C. Pyrido[3,46] 1,2,3-triazines 132
D. Pyrido[4,311] 1,2,3-triazines 132
XI. Condensed with the Quinoline System 132
A. 1,2,3-Triazino [4,5-c]q uinolines 132
XII. Condensed with the Pyridazine Ring 133
A. Pyridazino[4,511] 1,2,3-triazines 133
XIII. Condensed with the Pyrazine Ring 133
A. Pyrazino[2,34] 1,2,3-triazines 133
XIV. Condensed with the Pyrimidine Ring 133
A. Pyrimido[5,4-d] 1,2,3-triazines 134
XV. Condensed with the 1,2,3-Triazine Ring 141
XVI. Condensed with the 1,2,4-Triazine Ring 141
A. 1,2,4-Triazino[6,54] 1,2,3-triazines I41
XVII. Condensed with the 1,2,3,4-Tetrazine Ring 142
VI. 1,2,3-Triazine Rings Condensed with Heterocycles through a Carbon
Atom and a Nitrogen Atom 143
I. Condensed with the Pyrrole Ring 143
A. Pyrrolo [ 1,2-c] 1,2,3-benzotriazines 143
11. Condensed with the Pyrazole Ring 143
A. Pyrazolo[ 1,5-c] 1,2,3-triazines I43
B. Pyrazolo[ 1,5-c] 1,2,3-benzotriazines 144
111. Condensed with the Indazole System 145
A. Benzo[5,6] 1,2,3-triazino[3,4-b]i ndazoles 145
IV. Condensed with the Imidazole Ring 146
A. Imidazo[ 1,2111 1,2,3-benzotriazines 146
B. Imidazo[ 3,411j 1,2,3-benzotriazines 146
V. Condensed with the Benzimidazole System 147
A. Benzimidazo[l,2-c] 1,2,3-triazines 147
VI. Condensed with the Naphth[l,211] imidazole System 150
A. Naphth[ 1',2':4,5] imidazo[ 1,2-c] 1,2,3-benzotriazines and
Naphth [ 2',1':4,5] imidazo [ 1,2-c] 1,2,3-benzotriazines 150
VII. Condensed with the Imidazo[4,5-b] pyridine System 15 1