The Chemistry of Functional Groups, Supplement C Edited by S. Patai and Z. Rappoport 0 1983 John Wilev & Sons Ltd c Supplement The chemistry of triple-bonded functional groups Part 2 Edited by SAULP ATAI and Zvr RAPPOPORT The Hebrew University, Jerusnleizi 1983 JOHN WILEY & SONS CHICHESTER - NEW YORK - BRISBANE -TORONTO - SINGAPORE An Interscience 8 Publication Copyright 0 1983 by John Wiley & Sons Ltd. All rights reserved. No part of this book may be reproduced by any means, nor transmitted, nor translated into a machine language without the written permission of the publisher. Library of Congress Cataloging in Publication Data: Main entry under title: The Chemistry of tripled-bonded functional groups. (The Chemistry of functional groups. Supplement; C) Includes bibliographical references and indexes. 1. Acetylene compounds. I. Pntai, Saul. 11. Rappoport, Zvi. 111. Series. QD305.HgC44 1982 547' .4 13 82-17355 ISBN 0 471 28032 1 (U.S. : set) ISBN 0 471 28030 5 (U.S. : v. 1) ISBN 0 471 28031 3 (US. : v. 2) British Library Cataloguing in Publication Data: The chemistry of triple-bonded functional groups. --(The chemistry of functional groups; Supplement C) 1. Chemical elements I. Patai, Saul 11. Rappoport, Zvi 111. Series 540 QD181 ISBN 0 471 28032 1 ISBN 0 471 28030 5 v.1 LSBN 0 471 28031 3 v.2 Typeset by Preface Ltd., Salisbury, Wiltshire, and printed in Great Britain Contributing Authors Z. B. Alfassi Department of Nuclear Engineering, Ben-Gurion University of the Negev, Beer Sheva, Israel 84120 Y. Amiel The Weizrnann Institute of Science, Rehovot, Israel R. A. Bartsch Department of Chemistry, Texas Tech University, Lubbock, Texas 79409, U.S.A. L. Batt Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen, AB9 2UE, Scotland G. Bianchi Institute of Organic Chemistry, University of Pavia, Italy I. G. Binev Institute of Organic Chemistry, Bulgarian Academy of Sciences, 111 3 Sofia, Bulgaria H. Bock Chemische Institute der Universitat Frankfurt, Niederurseler Hang, D-6000 Frankfurt/Main 50, W. Germany K. Bott Hauptlaboratorium der BASF Aktiengesellschaft, D-6700 Ludwigshafen, Federal Republic of Germany M. Charton Pratt Institute, Department of Chemistry, Brooklyn, New York 11205, U.S.A. A. J. Fatiadi Centre for Analytical Chemistry, National Measurement Laboratory, National Bureau of Standards, Washington, D.C. 20234, U.S.A. J. P. Ferris Rensselaer Polytechnic Institute, Troy, N.Y., U.S.A. Friedrich Chemisches Laboratorium, Albert-Ludwigs-Universitat, K. Albertstrasse 21, 7800 Freiburg 1. Br., Germany R. Gandolfi Institute of Organic Chemistry, University of Pavia, Italy T. L. Gilchrist Department of Organic Chemistry, University of Liverpool, England P. Grijnanger Institute of Organic Chemistry, University of Pavia, Italy F. Hibbert Department of Chemistry, King’s College, Strand, London WC2R 2LS, England H. Hogeveen Department of Organic Chemistry, The University, Nijenborgh 16, 9747 AG Groningen, The Netherlands W. D. Huntsman Ohio University, Athens, Ohio, U.S.A. M. G. K. Hutchins Temple University, Philadelphia, Pennsylvania, U.S.A. R. 0. Hutchins Drexel University, Philadelphia, Pennsylvania, U.S.A. I. N. Juchnovski Institute of Organic Chemistry, Bulgarian Academy of Sciences, 111 3 Sofia, Bulgaria V vi Contributing Authors C. A. Kingsbury Department of Chemistry, University of Nebraska, Lincoln, NE 68588, U.S.A. D. M. Kok Department of Organic Chemistry, The University, Nijenborgh 16, 9747 AG Groningen, The Netherlands J. B. Moffat Department of Chemistry and Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Waterloo, Waterloo, Ontario, Canada D. G. Morris Department of Chemistry, University of Glasgow, Glasgow G12 SQQ, U.K. M. P. Periasamy Mallinckrodt, Inc., St. Louis, Missouri, U.S.A. H. C. van der Plas Laboratory of Organic Chemistry, Landbouwhogeschool, Wagen i ngen , The Net her1a nds F. Roeterdink Laboratory of Organic Chemistry, Landbouwhogeschool, Wageningen, The Netherlands W. Runge Organisch-Chemisches Institut der Technischen Universitat Munchen, Germany L. I. Simandi Central Research Institute for Chemistry, Budapest, Hungary H. Stafast Chemische Institute der Universitat Frankfurt, Niederurseler Hang D-6000 Frankfurt/Main 50, W. Germany H. M. Walborsky Florida State University, Tallahassee, Florida, U.S.A. K. Yoshida Department of Chemistry, Faculty of Engineering Science, Osaka University, Toyonaka, Osaka 560, Japan K.-P. Zeller Institut fur Organische Chemie, Universitat Tubingen, Auf der Morgenstelle, D-7400 Tubingen, Germany H. Zollinger Technisch-Chemisches Laboratorium, Eidgenossische Tech- nische Hochschule (ETM), Zurich, Switzerland Foreword The present Supplement C contains material on triple-bonded functional groups, such as carbon-carbon triple bonds, cyano and isocyano groups and diazonium groups. These groups have been treated previously in the Chemistry of Functional Groups Series in the following volumes: The Chemistry of the Carbon-Carbon Triple Bond (2 parts, 1978); The Chemistry of Diazonium and Diazo Groups (2 parts, 1978). Arynes, heteroarynes and isocyanides were treated as triple-bonded compounds, and chapters on them are included in this volume. Some chapters intended for this supplementary volume did not materialize. These should have treated ‘photochemistry of the Cyano Group’; Triple bonds in Cyclo- additions’, ‘Compounds Containing C(CN)2 and Related Groups’ and ‘Metal Triple- bond Complexes’. We will be very grateful to readers who would call our attention to omissions or mistakes relating to this and other volumes in the series. SAUL PATAI Jerusalem, June 1982 ZVI RAPPOPORT 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 Chemistry of the Ether Litzknge 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 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 material 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 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. Therefore each of the authors is asked not 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 cotizplete coverage of the subject with overlap between chapters, 110 while at the same time preserving the readability of the text. The Editor set himself the goal of attaining reasorzcrble 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 quasi-monographic chapters. 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 deter- is Preface to the series X mination including chemical and physical methods, ultraviolet, infrared, nuclear magnetic resonance and mass spectra: a chapter dealing with activating and direc- tive 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 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 photo- chemistry, radiation chemistry, biochemical formations and reactions. 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 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 func- tional group of the title, may have special features so as to be best treated in a separate chapter, as e.g. ‘Polyethers’ in The Chemistry of the Ether Linkage, or ‘Tetraamino- ethylenes’ 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 non-delivery of chapters, or to new developments in the subject, sufficient material has accumulated for publication of a supplementary volume, containing material on related functional groups, this will be done as soon as possible. The overall plan of the volumes in the series ‘The Chemistry of Functional Groups’ includes the titles listed below: The Chemistry of Alkenes (two volumes) The Chemistry of the Carbonyl Group (two volumes) The Chemistry of the Ether Linkage The Chemistry of the Amino Group The Chemistry of the Nitro and Nitroso Groups (two parts) The Chemistry of Carboxylic Acids and Esters The Chemistry of the Curbon-Nitrogen Double Bond The Chemistry of the Cyano Group The Chemistry of Amides The Chemistry of the Hydroxyl Group (two parts) The Chemistry of the Azido Group The Chemistry of Acyl Halides The Chemistry of the Carbon-Halogen Bond (trvo parts) The Chemistry of Quinoiioid Compounds (two parts) The Chemistry of the Thiol Group (tii>op arts) The Chemistry of Amidines arid Imidates The Chemistry of the Hydrato, Azo and Azoxy Groups (twop arts) The Chemistry of Cyatiates and their Thio Derivatives (twop arts) The Chemistry of Diazonium and Diazo Groups (two parts) The Chemistry of the Cnrbon-Carbon Triple Bond (trvo parts) Supplement A: The Cfzemistryo f Double-bonded Fiinctional Groups (trvo parts) Preface to the series xi Supplement B: The Chemistry of Acid Derivatives (two parts) Supplement C: The Chemistry of Triple-bonded Functional Groups (two parts) The Chemistry of Ketenes, Allenes and Related Compounds (two ports) Supplement E: The Chemistry of Ethers, Crown Ethers, Hydroxyl Groups and tlzeir Sulphur Analogues (two parts) The Chemistry of the Sulphonium Group (twop arts) Supplement F: The Chemistry of Amino, Nitroso and Nitro Groups arid their Derivatives (twop arts) Titles in press: The Chemistry of Peroxides The Chemistry of Organometallic Compounds Supplement D: The Chemistry of Halides and Pseudo-halides 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- 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 Israei and overseas helped me in the solution of various major and minor matters, and my thanks are due to all of them, especially 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 Jerusalem, ISRAEL SAUL PATAI Contents 1 . Chiroptical properties of compounds containing triple-bcnded functional groups 1 W. Runge 2. Thermochemistry of the cyano and isocyano groups 49 L. Batt 3. Mass spectra of cyano, isocyano and diazo compounds 57 K.-P. Zeller 4. Infrared spectra of cyano and isocyano groups 107 I. N. Juchnovski and I. G. Binev 5. Photoelectron spectra of cyano compounds 137 H. Stafast and H. Bock 6. Radiation chemistry of triple-bonded molecules 187 Z. B. Alfassi 7. Electrochemistry of the cyano group 22 1 K. Yoshida 8. The directing and activating effects of triply bonded groups 269 M. Charton 9. Biological formation and metabolic transformations of compounds containing the cyano group 325 J. P. Ferris 10. Free-radical reactions involving the CEC group 341 Y. Amiel 11. Arynes 383 T. L. Gilchrist 12. Six-membered didehydroheteroarenes 421 H. C. van der Plas and F. Roeterdink 13. Oxidation of triple-bonded groups 51 3 L. I. Sirnandi 14. Reduction of triple-bonded groups 571 R. 0. Hutchins and M. G. K. Hutchins 15. Dediazoniations of arenediazonium ions and related compounds 603 H. Zollinger 16. Alkenediazonium compounds 671 K. Bott xiii xiv Contents 17. Acidity and proton transfer of cyanocarbon acids 699 F. Hibbert 18. Recent developments on nitrile oxides, nitrile sulphides and nitrile selenides 737 G. Bianchi, R. Gandoifi and P. Griinanger 19. Conformation of cyano and isocyano compounds 805 C. A. Kingsbury 20. Recent advances in isocyanide chemistry 835 H. Walborsky and M. P. Periasamy 21. Complexation of aryldiazonium ions by polyethers 889 R. A. Bartsch 22. Poly(diacety1enes) and polyyne polymers containing transition-metal atoms in the main chain 91 7 W. D. Huntsman 23. Cyclodimerization of alkynes and reactivity of aluminium halide 0 complexes of cyclobutadienes 981 H. Hogeveen and D. M. Kok 24. Structure of triple-bonded molecules 1015 J. B. Moffat 25. NMR spectra of acetylenes 1035 D. G. Morris 26. Preparation and synthetic applications of cyano compounds 1057 A. J. Fatiadi 27. General and theoretical properties of triple-bonded molecules 1305 J. B. Moffat 28. Recent advances in the synthesis of triple-bonded groups 1345 K. Friedrich Author index 1391 Subject index 1491