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) \ / c=c / \ 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