The Alkenes: Volume 2 (1970)

677 Pages·1970·17.92 MB·English

The Chemistry of Alkenes
Edited by Jacob Zabicky
Copyright 0 1970 John Wiley & Sons Ltd. All rights reserved.
The chemistry of
aBkenes
Volume 2
THE CHEMISTRY OF FUNCTIONAL GROUPS
A series of advanced treatises under the general editorship of
Professor Saul Parai
The chemistry of alkeries (published 2 volumes)
The Chemistry of the carbonyl group (published)
The chemistry of the ether linkage (published)
The chemistry of the amino group (published)
The chemistry of the nitro and nitroso groups (published in 2 parts)
The chemistry of carboxylic acids and esters (published)
The chemistry of the carhon-nitrogen double bond (published)
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Volume 2
Edited by
JACOB ZABICKY
Instilute for Fibres and Forest Produts Research, .Jemalem
and
The WeizmannI nstitute of Science, Rehovoth, Isi,ael
19 70
INTERSCIENCE PUBLISHERS
a division of John Wiley & Sons
LONDON - NEW YORK - SYDNEY - TORONTO
First published 1970 John M’ilcy & Sons Ltd.
All Rights Rcscrved. No part of this publication
may be reproduced, stored in a retrieval system,
or transmitted, in any form or by any means
electronic, mcchanical photocopying, recording
or othcwise, without tlic prior writtcn pcrmis-
sion the Copyright owner.
of
Library of Congress Catalogue Card No. 64-25218
ISBN 0 471 98050 1
Made and printed in Great Britain by
1ViUiarn Clowar and Sons, Liniiled, London and Beccles
To my parents
far yet so close
away and
Jean-Francois Biellniann FacultC dcs Sciences, Strasbourg, France.
Marvin Charton Pratt Institute, Brooklyn, USA.
N.Y.,
K. J. Crowley Trinity College, Dublin, Ireland.
J. H. Goldstein Emory University, Atlanta, Georgia, U.S.A.
Morton A. Golub Ames Research Center, National Aeronautics
Space Administration, Moffett Field, Cali-
st
fornia, U.S.A.
Henri Hemmer SociCtt Nationale des Petroles d’Aquitanc,
Lacq, France.
Akira Kasahara Yamagata University, Yamagata, Japan.
Jacques Levisalles FacultC des Sciences, Nancy, France.
A. G. Loudon University College, London, England.
Allan Maccoll University College, London, England.
Kenneth Mackenzie University of Bristo:, Bristol, England.
P. H. Mazzocchi University of Maryland, Coilege Park, Mary-
land, U.S.A.
G. G. Meisels Department of Chemistry, University of
Houston, Texas, U.S.A.
Sekio Mitsui Tohoku University, Sendai, Japan.
Herman G. Richey, Jr. Pennsylvania State University, University
Park, Pennsylvania, U.S.A.
v. s. Watts Emory University, Atlanta, Georgia, U.S.A.
The main purposes for a second volume dealing with the chemistry of
the carbon-carbon double bond, were to cover the aspects that were
left out in the previous volume because of authors having failed to
deliver their contributions and to widen its coverage.
The topics of electrophilic additions and biological aspects of the
double bond seem to have a fate of their own as, again, the commit-
ment to writc these chapters was not fulfilled by a second grou:, of
authors.
The material included in the present volume can be classified into
three main groups:
Gemral-!.kweticaI: to this group belongs a chapter on n.m.r. spectro-
scopy.
Chemical behauiour :t his is dealt with in chapters on rearrangements,
hydrogenation, olefinic ions, complexes with transition metals, and
the effects of various types of radiation.
Related compounds :t hese are treated in chapters on olefinic polymers
and cyclopropanes.
I am indebted to Dr. M. Levin, director of the Institute of Fibres
and Forest Products Research, for enabling me to carry out part of the
present work during my stay in that Institute. Finally, I would like
to thank Prof. Saul Patai for help and guidance, and my wife for
his
her constant encouragement and patience.
ZABICKY
JACOB
Jerusalem and Rehovoth, 1968
The Chemistry of the Functional Groups
Preface to the series
The series ‘The Chemistry 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 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 Chemistry 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 reactiom 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
cther group, but the primary subject matter is not the whole molecule,
but the C-0-C functional group.
A further rcstriction in the treatment of the various functional
groups in thcse volumcs is that material included in easily and gen-
erally 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
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 balanccd trea tmcnt of the subject. Therefore each
of the authors is asked not to Sive an encyclopaedic coverage of his
subject, but to concentrate on the most important recent develop-
ments and mainly material that has not been adequately covered
011
by reviews or othcr 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 thc goal of attaining
reasoncvhle coverage with moderate ovcrlap, with a miiiinium of
xii Preface to the Scrics
cross-references between the chapters of each volume. In this manner,
sufficientf reedom is given to each author to produce readable quasi-
monographic chapters.
The general plan of each volumc 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.e. 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 or in
conjuxtion with other reagents.
(e) Special topics which do not fit any of the above sections, such
photochemistry, radiation chemistry, biochemical formations and
as
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 ‘Thioketones’ is included in the volume The C/zenrishy of the
Curbonyl Group, and a chapter on ‘Ketenes’ is included in the volume
The Chemistry of dlkenes). 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 ChemzFtry 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
Prcfacc to the Series xiii
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 non-delivery
of chapters, or to new developmznts in the subject, sufficient material
has accumulated for publication of an additional part, this will bc
done as soon as possible.
It is hoped that future volumes in the series ‘Thc Chemistry of the
Functional Groups ’ will include the topics listed below :
TfieC hemistry of the Alkenes (published in two volumes)
The Chemistry of tfie C‘arboiiyl Group (Volume 1 published, Volume 2 in
preparation)
The Chemistry of the Ether Linkage (published)
The ChemistrrJ of ihe Amino Group (published)
The Chemistry of the Nitro and Nitroso Group (publtshd in two parts)
The Chemistry of Carboxglic Acids and Esters (published)
TIEC hemistry of tfie Carbon-Nitrogen Double Bond (published)
The Chemistry of lhe Cyan0 Group (in press)
Tlte Chemtstry of‘ Ihe Amides (in tress)
The Chemistry of the Carbon-Halogen Bond
The Chemistry of :he N’droxgl Group (inp ress)
Th Chemistry of the Carbon-Carbon Triple Bond
The Chemistry of the Azido Gioup (in Ireparation)
T ~CPhem istry of Imidoates and Amid‘ines
The Chemistry of the Thiol G~oup
The Chemistry of the H’drazo, Azo and Azoxg Groups
The Chemistry of Carbonyl Halides (inp reparation)
The Chemistry of tire SO, SO2, -SO2E and -S3,f-I Grouts
The Chemistry of the -OCN, -NCO and -SCN Croups
The Chemistry of the -PO3H2 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 started, let alone
have
continued, without the support of many persons. First and foremost
among these is Dr. Arnold M’eissberger, whose reassurance and trust
encouragcd 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