Table Of ContentThe Chemistry of the carbon-nitrogen double bond
Edited by Saul Patai
Copyright 0 1970 by John Wiley & Sons Ltd. All rights reserved.
The chemistry of the
carbon-nitrogen double bond
THE CHEMISTRY OF FUNCTIONAL GROUPS
A series of adunnced treatises under the general editors4 of
Professor Saul Patai
The chemistry of alkenes (2 volumes)
The chemistry of the carbonyl group (2 volumes)
The chemistry of the ether linkage
The chemistry of the amino group
The chemistry of the nitro and nitroso groups (2 parts)
The chemistry of carboxylic acids and esters
The chemistry of the carbon-nitrogen double bond
The chemistry of amides
The chemistry of the cyano group
The chemistry of the hydroxyl group (2 parts)
The chemistry of the azido group
The chemistry of acyl halides
The chemistry of the carbon-halogen bond (2 parts)
The chemistry of the quinonoid compounds (2 parts)
The chemistry of the thiol group (2 parts)
The chemistry of the hydrazo, azo and azoxy groups (2 pxts)
The chemistry of amidines and imidates
The chemistry of cyanates and their thio derivatives (2 parts)
The chemistry of diazonium and diazo groups (2 parts)
The chemistry. of the carbon-arbon triple bond (2 parts)
Supplement A: The chemistry of double-bonded functional groups (2 parts)
Supplement The chemistry of acid derivatives (2 parts)
B:
The chemistry of the
Edited by
SAULP ATAI
The Hebrew University
Jerusaleni, Israel
1970
JOHN WILEY & SONS
CHICHESTER - NEW - BFUSBANE - TORONTO
YORK
An Interscience CB Publication
First published 1970 John Wilcy & Sons Ltd.
All Rights Reserved. No part of this publica-
tion may be reproduced. stored in a rctricval
system. or transmitted, in any form or by any
mearis electronic. mechanical photocopying.
recording or otherwise, without the prior
written permission of the Copyright owner.
Library of CongrcssCatalog Card 70- I66
No. I04
ISBN (1471 66942
3
Reprinted Scptembcr 1979
Printed in Great Britain by
Page Bros (Norwich) Ltd.
Mile Cross Lane. .Nortc,ich
Contributing authsPs
Jean-Pierre Anselme University of Massachusetts, Boston, U.S.A,
R. Bonnett Queen Mary College, London, England.
Albert Bruylants UniversitC de Louvain, Belgium.
David J. Curran University of Massachusetts, Amherst, Massa-
chusetts, U.S.A.
Shlomo Dayagi Tel-Aviv Univeristy, Israel.
Yair Degani M'eizmann Institute of Science, Rehovoth,
Israel.
Thomas Finley Eastman Kodak Company, Rochester, New
K.
York, U.S.A.
Kaoru Harada University of Miami, Florida, U.S.A.
Henning Lund University of Aarhus, Denmark.
C. G. McCarty West Virginia University, Morgantown.
U.S.A.
Mrs. E. FeytmaEts-de Universitt. de Louvain, Belgium.
Medicis
R. J. Morath College of St. Thomas, St. Paul, Minnesota,
U.S.A.
C. Sandorfy UniversitC de MontrPal, Canada.
Sidney Siggia University of Massachusetts, Amherst, Massa-
chusetts, U.S.A.
J. W. Smith Bedford College, London, England.
Gardner W. Stacy Washington State University, Pullman,
Washington, U.S.A.
J. Tong Eastman Kodak Company, Rochester, New
L. K.
York, U.S.A.
Gunnar Wettermark Institute of Physical Chcmistry, UEiversity of
Uppsala, Sweden.
V
The general plan of the prescnt volumc is again the same as des-
cribed in the Preface to the series, printed on the following pages.
This volume was originally planned to consist of seventeen chapters,
out of which three did not materialize. These should have been
chaptcrs on the “Directing and Activating Effects” and on the
‘‘ Syntheses and Uses of Isotopically Labelled Azoniethine Groups”,
both in which cases the scarcity of the information available on the
subjects was the decisive factor, and a chapter on the “Biological
Formation and Reaction of the Azomethine Groups”.
SAULP ATAI
Jerusalem, September 1969
vii
The Chemistry the Functional Groups
0%
The series ‘The Chcmistry of the Functional Groups’ is planned to
cover in each volume all aspects of the chemistry of one of the impor-
tant functional groups in organic chemistry. The emphasis is laid on
the fkctional group treated and on the eflects which it exerts on the
chcmical and physical properties, primarily in the immediate vicinity
of the group in question, and sccondxily on the bchaviour of the whole
of the group in question, and secondarily on the behaviour of thc
whole molecule. For instance, the volume T/ie C/zemistgj of the Ether
Linkage deals with reactions in which the C-0-C group is involved,
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 matier is not the whole mole-
cule, but the C-0-C functional group.
A further restriction in the treatment of the various functional
groups in these volumes is that material included in easily and gen-
erally zvailable secondary or tertiary sources, such as Chemical
Reviews, Quarterly Reviews, Organic Rcactions, various ‘Advances’
and ‘Progress’ series as well as textbooks (i.e. in books which are
usually 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. Thzrefore each
of the authors is asked not to give an encyclopaedic coverage of his
subject, but to concentrate on the most important recent develop-
ments 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 complete coverage of the subject with no
overlap between chapters, while at the same time preserving the read-
ability of the text. The Editor set himself the goal of attaining
ix
Preface to the Series
X
reasonable coverage with moderate overlap, with a minimuin of cross-
references between the chapters of each volume. In this manner,
sufficient freedom is given to each author to produce readable quasi-
monographic chapters.
The general plan of each volume includes the following main
sections :
(a) An introductory chapter dealing with the general and theo-
retical aspects of the group.
(b) One or more chapters dealing with the formation of the func-
tional 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.c. a chapter dealing with qualitative and
quantitative methods of determination including chemical and physi-
cal 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 applicable).
(d) Chapters on the reactions, transformations and rearrange-
ments which the functional group can undergo, either alone cr 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
reactions. Depending on the nature of each functional group treated,
these special topics may include short monographs on related func-
tional groups on which no separate volume is planned (e.g. a chapter
on ‘Thicketones’ is included in the volume The Chemistry of the
Carbonyl Group, and a chapter on ‘Ketenes’ is included in the volume
The Chemistry 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.
Prcfacc to the Scrics xi
Moreover, a serious problem is caused by authors who deliver their
maiiuscript late or not at all. In order to overcome this problem at
least to some extent, it was dccided 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 non-delivery
of chapters, or to new developments in the subject, sufficient material
has accumulated for publication of an additional part, this will be
done as soon as possible.
It is hoped that future volumes in the series ‘The Chemistry of the
Functional Groups’ will include the topics listed below:
The Cfiemzktryo f the Alkenes (published)
Thc Chemistry of the Carboy1 Group (published)
The Chemistry of the Ether Linkage (published)
The Chemistry of the Amino Group (published)
TJze Chemistv of the Nitro and Nitroso Group (Part I, published, Part 2,
in preparation)
The Chemistry CarboxJvlic Acih and Esters (published)
of
The Chemistry of the Carbon-Nitrogen Double Bond (published)
The Chemistry of the Cyano Group (inp ress)
The Chemistry of the Amides (in press)
The Clremistry of the Carbon-Halogen Bond
The Chemistry of the Hydroxyl Group (inp ress)
The Chemistry of the Carbon-Carbon Triple Bond
The Chemistry of the Azido Group (inp reparation)
The Chemistry of Imidoates and Arnidines
The Chemistry o f the Thiol Group
The Chemistry of the Hydrazo, Azo and rlzoxy Groups
The Chemistry of Carbonyl Halides
The Chemistry of the SO, SOz, -SO,H and -S03H Groups
The Chemistry of the -OClV, -NCO and -SCN Groups
The Chemistry of the -P03H2 and Related Groups
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
continued, 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-
sii Preface to the Series
members of the Publisher also rendered me invaluable aid (but un-
fortunately their code of ethics does not allow me to thank them by
name). Many of my friends and colleagues in Jerusalem helped me in
the solution of various major and minor matters and my thanks are
due especially to Prof. Y. Liwschitz, Dr. 2. Rappoport and Dr. J.
Zabicky. Carrying out such a long-range project would be quite im-
possible without the non-professional but none the less essential
participation and partnership of my wife.
The Hebrew University, SAULP ATAI
Jerusalcm, ISRAEL
