The 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