Table Of ContentThe Chemistry of’ The H-vdrazo, Azo and Azoxy Croups
Edited by Saul Patai
Copyright 0 1975, by John Wiley & Sons, Ltd. All rights reserved
The chemistry of
the hydrazo, azo and
azoxy groups
Part 1
Edited by
SAUL PATAI
The Hebrew University, Jerusalem
1975
JOHN WILEY & SONS
LONDON - NEW YORK - SYDNEY - TORONTO
An Interscience 0P ublication
Copyright 0 1975, by John Wiley & Sons, Ltd.
All rights reserved.
No part of this book may be reproduced by any means, nor
translated, nor transmitted into a machine language without
the written permission of the publisher.
Library of Congress Cataloging in Publication Data:
Patai, Saul
The chemistry of the hydrazo, azo, and azoxy groups.
{The Chemistry of functional groups)
An Interscience Dubhation.'
Includes indexes.'
1.Azocompounds. 2,Azoxycompounds. 1.Title.II.Series.
QD341.AgP36 547'.043 75-2194
ISBN 0 471 66926 1 (Pt. 1)
ISBN 0 471 66927 X (Pt. 2)
ISBN 0 471 66924 5 (Set)
Printed in Great Britain by J W Arrowsmith Ltd,
Bristol, BS3 2NT.
c or nt rib uti n g A uth ors
R. Allmann Philipps University, Lahnbergc, 355 Marburg, Ger-
many
J.-P. Anselme University of Massachusetts at Boston, Boston,
Massachusetts 02125, U.S.A.
K. G. Boto James Cook University of North Queensland, Towns-
ville, Australia 481 1
M. I. Bruce University of Adelaide, South Australia 500 1
Buncel Queen’s University, Kingston, Ontario, Canada
E.
R. A. Cox Queen7sU niversity, Kingston, Ontario, Canada
A. J. Dolenko Eastern Forest Products Laboratory, Canadian Fores-
try Service Environment Canada, Ottawa, Ontario,
Canada
H. J. Drewer Avondale College, Cooranbong, N.S.W. 2265, Austra-
lia
Goodall The University, Bristol, England
B. b.
D. A. R. Happer University of Canterbury, Christchurch, New Zealand
A. Hegarty University College, Cork, Ireland
F.
A. Horowitz Soreq Nuclear Research Centre, Yavne, Israel
G. Ibaraki University, Mito, Japan
Koga
Ibaraki University, Mito, Japan
N. Koga
P. Krueger University of Calgary, Calgary, Alberta, Canada
J.
K. Mackenzie University of Bristol, Bristol, England
T. Miyadera Central Research Laboratories, Sankyo Co., Ltd.,
Tokyo, Japan
8. T. Newbold University of Moncton, Moncton, New Brunswick,
Canada
L. A. Rajbenbach Soreq Nuclear Research Centre, Yavne, Israel
M. 8. Robin Bell Laboratories, Murray Hill, New Jersey, U.S.A.
R. Shaw Stanford Research Institute, Menlo Park, California,
U.S.A.
Y. Shvo Tel-Aviv University, Tel-Aviv, Israel
F. Snatzke University of the Ruhr, Bochum, Germany
G. Snatzke University of the Ruhr, Bochum, Germany
vi Contributing Authors
J. C. Stowell Louisiana State University in New Orleans, Louisiana,
U.S.A.
S. W. Tam The Chinese University of Hong Kong, Shatin, N.T.,
Hong Kong
F. G. Thomas James Cook University of North Queensland, Towns-
ville, Australia 481 1
J. W. Tirnberlake Louisiana State University in New Orleans, Louisiana,
U.S.A.
J. Vaughan University of Canterbury, Christchurch, New Zealand
Foreword
The present volume, ‘The Chemistry of the Hydrazo, Azo and Azoxy
Groups’ is organized and presented on the same general lines as the other
volumes of the series and which are described in the ‘Preface to the series’
printed on ;lie following pages.
The subject matter of this volume does not include either diazonium
salts or diazo-alkanes. These groups will be treated in a separate forth-
coming volume of the series. In addition it was decided not to treat azo
dyes as such extensively since this would have enlarged the volume to un-
reasonable proportions while recent and satisfactory treatises exist on this
subject.
The plan of the present volume included also a chapter on ‘Detection
and Determination of Hydrazo, Azo and Azoxy Groups’ which however
owing to the illness of the author, did not materialize.
Some additional material on the Azo and Azoxy Groups will also be
available soon in the first supplementary volume of the series now in the
press which will include material on double-bonded groups. While this
supplementary volume will treat mainly the C=C, C=O and C=N groups
it will also treat some aspects of the N=N groups in several of its chapters.
Jerusalem, January 1975 SAUL PATAI
vii
The Chemistry of Functional Groups
Preface to the series
The series ‘The Chemistry of Functional Groups’ is planned to cover
in each volume all aspects of the chemistry of one of the important functional
groups in organic chemistry. The emphasis is laid on the functional group
treated and on the effects which it exerts on the chemical and physical
properties, primarily in the immediate vicinity of the group in question,
and secondarily on the behaviour of the whole molecule. For instance, the
volume The Cliemistry of the Ether Linkage deals with reactions in which the
C-0-C group is invo!ved, as well as with the effects of the C-0-C
group on the reactions of alkyl or aryl groups connected to the ether oxygen.
It is the purpose of the volume to give a complete coverage of all properties
and reactions of ethers in as far as these depend on the presence of the
ether group, but the primary subject matter is not the whole molecule,
but the C-0-C functional group.
A further restriction in the treatment of the various functional groups
in these volumes is that materiai included in easily and generally available
secondary or tertiary sources, such as Chemical Reviews, Quarterly
Reviews, Organic Reactions, various ‘Advances’ and ‘Progress’ series as
well as textbooks (i.e. in books which are usuzlly found in the chemical
libraries of universities and research institutes) should not, as a rule, be
repeated in detail, unless it is necessary for the balanced treatment of the
subject. Therefore each of the authors is asked ,rot to give an encyclopaedic
coverage of his subject, but to concentrate on the most important recent
developments and mainly on material that has not been adequately covered
by reviews or other secondary sources by the time of writing of the chapter,
and to address himself to a reader who is assumed to be at a fairly advanced
post-graduate level.
With these restrictions, it is realized that no plan can be devised for a
volume that would give a coinplete coverage of the subject with no overlap
between chapters, while at the same time preserving the readability of the
text. The Editor set himself the goal of attaining reasonable coverage
with moderate overlap, with a minimum of cross-references between the
chapters of each volume. In this manner, sufficient freedom is given to
each author to produce readable quazi-monographic chapters.
ix
X Preface to the serics
The general plan of each volume includes the following main sections:
(a) An introductory chapter dealing with the general and theoretical
aspects of the group.
(b) One or more chapters dealing with the formation of the functional
group in question, either from groups present in the molecule, or by
introducing the new group directly or indirectly.
(c) Chapters describing the characterization and characteristics of the
functional groups, i.e. a chapter dealing with qualitative and quantitative
methods of determination including chemical and physical methods,
ultraviolet, infrared, nuclear magnetic resonance and mass spectra : a
chapter dealing with activating and directive effects exerted by the group
and/or a chapter on the basicity, acidity or complex-forming ability of the
group (if appiicable).
(d) Chapters on the reactions, transformations and rearrangements
which the functional group can undergo, either alone or in conjunction
with other reagents
(e) Special topics which do not fit any of the above sections, such as
photochemistry, radiation chemistry, biochemical formations and reac-
tions. Depending on the nature of each functional group treated, these
special topics may include short monographs on related functional groups
on which no separate volume is planned (e.g. a chapter on ‘Thioketones’
is included in the volume The Clienzistry of the Carbonyl Group, and a
chapter on ‘Ketenes’ is included in the volume The Chenzistry of Alkenes).
In other cases, certain compounds, though containing only the functional
group of the title, may have special features so as to be best treated in a
separate chapter, as e.g. ‘Poly ethers’ in The Chemistry of the Ether Linkage,
or ‘Tetraaminoethylenes’ in The Chemistry of the Amino Group.
This plan entails that the breadth, depth and thought-provoking nature
of each chapter will differ with the views and inclinations of the author
and the presentation will necessarily be somewhat uneven. Moreover,
a serious problem is caused by authors who deliver their manuscript late
or not at all. In order to overcome this problem at least to some extent,
it was decided to publish certain volumes in several parts, without giving
consideration to the originally planned logical order of the chapters.
If after the appearance of the originally planned parts of a volume it is
found that either owing to Eon-delivery of chapters, or to new develop-
ments in the subject, sufficient material has accumulated for publication
of an additional part, this will be done as soon as possible.
Preface to the series xi
The overall plan of the volumes in the series ‘The Chemistry of Functional
Groups’ includes the titles listed below :
The Chemistry of Alkenes (published in two volumes)
The Chemistry of the CarbonyI Group (published in two volumes)
The Chemistry of the Ether Linkage (published)
The Chemistry of the Amino Group (published)
The Chemistry of the Nitro and the Nitroso Group (published in two patts)
The Chemistry of Carboxylic Acids and Esters (published)
The Chemistry of the Carbon-Nitrogen Double Bond (published)
The Chemistry of the Cyano Group (published)
The Chemistry of Amides (published)
The Chemistry of the Hydroxyl Group (published in two parts)
The Chemistry of the Azido Group (published)
The Chemistry of Acyl Halides (published)
The Chemistry of the Carbon-Halogen Bond (published in two parts)
The Chemistry of the Quinonoid Compounds (published in two parts)
The Chemistry of the Thiol Group (published in two parts)
The Chemistry of the Carbon-Carbon Triple Bond
The Chemistry of Amidines and Imidates (in press)
The Chemistry of the Hydrazo, Azo and Azoxy Groups (published)
The Chemistry of the Cyanates and their Thio-derivatives (in preparation)
The Chemistry of the Diazonium and Diazo Groups (in preparation)
Supplementary Volume on the Chemisiry of Double-bonded Groups (in
press)
Advice or criticism regarding the plan and execution of this series will
be welcomed by the Editor.
The publication of this series would never have started, let alone con-
tinued, without the support of many persons. First and foremost among
these is Dr. Arnold Weissberger, whose reassurance and trust encouraged
me to tackle this task, and who continues to help and advise me. The
efficient and patient cooperation of several staff-members of the Publisher
also rendered me invaluable aid (but unfortunately their code of ethics
does not allow me to thank them by name). Many of my friends and
colleagues in Israel and overseas helped me in the solution of various
major and minor matters, and my thanks are due to all of them, especia!ly
to Professor Z. Rappoport. Carrying out such a long-range project would
be quite impossible without the non-professional but none the less essential
participation and partnership of my wife.
The Hebrew University, SAULP ATAI
Jerusalem, IsRAEL
contents
1. Electronic structures of the azo, azoxy and hydrazo groups 1
M. B. Robin
2. Structural chemistry 23
R. Allmann
3. Thermochemistry of hydrazo, azo and azoxy groups 53
R. Shaw
4. Preparative procedures 69
J. W. Timberlake and J. C. Stowell
5. Mass spectra of hydrazo, azo and azoxy compounds 109
S. W. Tam
6. Chiroptical properties of the azo and the azoxy zhromo-
phores 129
G. Snatzke and F. Snatzke
7. Basicity, hydrogen bonding and complex formation nvolving
hydrazo, azo and azoxy groups 153
P. J. Krueger
8. Directing and activating effects 225
D. A. R. Happer and J. Vaughan
9. The transition metal chemistry of azo compounds 259
M. I. Bruce and B. Goodall
L.
10. Radiation chemistry of hydrazo and azo compounds 31 3
A. Horowitz and L. A. Rajbenbach
11. Formation and fragmentation of cyclic azo compounds 329
K. Mackenzie
12. The electrochemistry of azcxy, azo and hydrazo compounds 443
F. G. Thomas and K. G. Boto
13. Biological formation and reactions of hydrazo, azo and
azoxy groups 495
T. Miyadera
14. Oxidation and synthetic uses of hydrazo, azo and azoxy
corn pou nds 541
B. T. Newbold
...
Xlll
xiv Contents
15. Reduction and synthetic uses of hydrazo, azo and azoxy
compounds 599
B. T. Newbold
16. Ionic reactions involving hydrazo, azo and azoxy groups 643
A. F. Hegarty
17. Syntheses and uses of isotopically labelled hydrazo, azo and
azoxy compounds 725
A. J. Dolenko and E. Buncel
18. Rearrangements of hydrazo, azoxy and azo compounds 775
R. A. and E. Buncel
Cox
19. Radical reactions of azo, hydrazo and azoxy compounds 861
G. Koga, N. Koga and J.-P. Anselme
The photochemistry of the hydrazo, azo and azoxy groups 935
20.
R. J. Drewer
21. Conformational analysis of hydrazines 1017
Y. Shvo
Author index 1097
Subject index 1157
