Halides, Pseudo-Halides and Azides: Volume 2 (1983)

938 Pages·1983·20.37 MB·English

The Chemistry of Functional Groups, Supplement D
Edited by S. Patai and 2. Rappoport
0 1983 John Wiley & Sons Ltd
Supplement D
The chemistry of
halides, pseudo-halides
and azides
Part 2
Edited by
SAUL PATAI
and
ZVIR APPOPORT
The Hebrew University, Jerusalem
1983
JOHN WILEY & SONS
CHICHESTER - NEW YOKK - BRISBANE - TORONTO - SINGAPORE
An Znterscience @ 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:
The Chemistry of halides, pseudo-halides, and azides.
(The Chemistry of functional groups. Supplement: D)
‘An Interscience publication.’
Includes bibliographical references and indexes.
1. Halides. 2. Azides. I. Patai, Saul. 11. Rappoport,
Zvi. 111. Series.
QD165.C48 1983 546l.73 82-23908
ISBN 0 471 10089 7 (se;)
ISBN 0 471 10087 0 (v. 1)
ISBN 0 471 10088 9 (v. 2)
British Library Cataloguing in Publication Data:
Supplement D: the chemistry of halides, pseudohalides
and aides.-(The Chemistry of functional groups)
1. Halogens 2. Chemistry, Organic
I. Patai, Saul 11. Rappoport, Zvi 111. Series
547l.02 QD165
ISBN 0 471 10089 7 (set)
ISBN 0 471 10087 0 (v. 1)
ISBN 0 471 10088 9 (v. 2)
Typeset by Preface Ltd., Salisbury, Wiltshire,
and printed in Great Britain.
Contributing authors
E. Baciocchi Department of Chemistry, University of Perugia, Perugia, Italy
J. Y. Becker Department of Chemistry, Ben-Gurion University of the Negev,
Beer Sheva, Israel
K. Berei Central Research Institute for Physics, PO Box 49, H-1525
Budapest, Hungary
H. Bock Institute of Inorganic Chemistry. Johann Wolfgang Goethe
University, Niederurseler Hang, D-6000 Frankfurt (M) 50,
West Germany
J. M. Brittain Department of Chemistry, University of Auckland, Private Bag,
Auckland, New Zealand
N. De Kimpe Laboratory of Organic Chemistry, Faculty of Agricultural
Sciences, State University of Gent, Coupure 533, B-9000 Gent,
Belgium
P. 6. D. de la Mare Department of Chemistry, University of Auckland, Private Bag,
Auckland, New Zealand
J.-M. Dumas Laboratoire de Physico-Chimie des Ditlectriques, FacultC des
Sciences Fondamentales et Appliqutes, UniversitC de Poitiers,
86022 Poitiers Cedex, France
L. K. Dyall Department of Chemistry, University of Newcastle, New South
Wales 2308, Australia
A. Foucaud Department of Crystal Physics and Structural Chemistry,
University of Rennes I, Avenue du GCnCral Leclerc, 35042
Rennes Cedex, France
D. M. Goldish Department of Chemistry, California State University, Long
Beach, California 90840, USA
M. Gomel Laboratoire de Physico-Chimie des DiClectriques, FacultC de
Sciences Fondamentales et AppliquCes, UniversitC de Poitiers,
86022 Poitiers Cedex, France
M. Guerin Laboratoire de Physico-Chimie des Ditlectriques, FacultC de
Sciences Fondamentales et AppliquCes, UniversitC de Poitiers,
86022 Poitiers Cedex, France
R. R. Gupta Department of Chemistry, University of Rajasthan, Jaipur
302004, India
E. Hadjoudis Solid State Chemistry Laboratory, Department of Chemistry,
Greek Atomic Energy Commission, Nuclear Research Centre
‘Demokritos’, Aghia Paraskevi, Attiki, Athens, Greece
V
vi Contributing authors
A. Horowitz Soreq Nuclear Research Centre, Yavne, Israel
M. Hudlicky Department of Chefiistry., Virginia Polytechnic Institute and
State University, Blacksburg, Virginia 24061, USA
Hudlicky Department of Chemistry, Virginia Polytechnic Institute and
T.
State University, Blacksburg, Virginia 24061, USA
T. R. Jones Department of Chemistry, Brock University, St Catherines,
B.
Ontario, Canada L2S 3A1
M. Kaftory Department of Chemistry, Technion-Israel Institute of
Technology, Haifa, Israel
D. N. Kevill Department of Chemistry, Northern Illinois University, DeKalb,
Illinois 60115, USA
G. F. Koser Department of Chemistry, University of Akron, Akron, Ohio
44325, USA
G. Lodder Gorlaeus Laboratories, University of Leiden, Leiden, The
Netherlands
A. C. Lucken Physical Chemistry Department, 30 Quai E. Ansermet, 1211
E.
Geneva, Switzerland
G. Marchese Istituto di Chimia Organica, Universith di Bari, Bari, Italy
A. Y. Meyer Department of Organic Chemistry, Hebrew University,
Jerusalem, Israel
J. M. Miller Department of Chemistry, Brock University, St Catherines,
Ontario, Canada L2S 3A1
H. W. Moore Department of Chemistry, University of California, Irvine,
California 92717, USA
F. Naso Istituto di Chimia Organica, Universith di Bari, Bari, Italy
R. K. Norris Department of Organic Chemistry, University of Sydney,
Sydney, New South Wales 2006, Australia
B. E. Smart Central Research and Development Department, Experimental
Station, E. I. du Pont de Nemours & Co., Wilmington, Delaware
19898, USA
L. Vasaros Central Research Institute for Physics, PO Box 49, H-1525
Budapest, Hungary
R. Verhe Laboratory of Organic Chemistry, Faculty of Agricultural
Sciences, State University of Gent, Coupure 533, B-9000 Gent,
Belgium
P. Weyerstahl Technische Universitat Berlin, Institut fur Organische Chemie,
D-1000 Berlin 12, German Federal Republic
K. Wittel Institute of Inorganic Chemistry, Johann Wolfgang Goethe
University, Niederurseler Hang, D-6000 Frankfurt (M) 50,
West Germany
M. Zupan Department of Chemistry and ‘Joief Stefan’ Institute,
‘E. Kardelj’ University of Ljubljana, Murnikova 6 - PO Box 537,
61001 Ljubljana, Yugoslavia
Foreword
This Supplement D contains material on halides, pseudo-halides and azides. The same
functional groups have been treated previously in the following main volumes of the
Chemistry of the Functional Groups series:
The Chemistry of the Azido Group (1971)
The Chemistry of the Carbon-Halogen Bond (2 parts, 1973)
The Chemistry of Cyanates and their Thio Derivatives (2 parts, 1977)
Chapters which were also intended to appear in this volume, but did not materialize
were the following: “Advances in the preparation and uses of azides”; “Recent
advances biological reactions involving halides and pseudo-halides”; and “Syntheses
in
and uses of isotopically labelled halides and azides”. We hope that these chapters will
be included in a future supplementary volume, which should be published in several
years’ time when the amount of new and unreviewed material justifies this.
The present volume concludes the first set of supplementary volumes (Supplements
A, B, C, D, E and F) which cover among themselves all the subjects treated in the
Functional Groups series.
We will be very grateful to readers who would call our attention to omissions or
mistakes in this and other volumes in the series.
SAUL PATAI
ZVI RAPPOPORT
Jerusalem, October 1982
vii
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 fliiictional group treated ai:d 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 Chet~iistryo f 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 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 tiot 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 complete coverage of the subject with ti0 overlap between chapters,
while at the same time preserving the readability of the text. The Editor set himself the
goal of attaining reasotinble 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 producc 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
qroup.
(b) Orie or more chapters dealing with the formation of the functional group in
question, either from groups present in the molec.;!e, 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 quantitstive methods of deter-
is
X Preface to the series
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 o:! re!ated functional groups on which no separate volume is planned
(e.g. ;I chapter on ‘Thioketones’ is included in the volume The Chemistry of the
Carhonyl 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 Carbon-Nitrogen Double Bond
The Chemistry of the Cyan0 Group
The Chemistry of Amides
The Chemistry of the Hydrosyl Group (two piirts)
The Chemistry of the Azido Group
The Chemistry of Acyl Hiilides
The Chemistry of the Carbon-Halogen Bond (two parts)
The Chemistry of Quitlonoid Compounds (nvo ports)
The Chemistry of the Thiol Group (two parls)
The Chemistry of Aniidines arid Iinidates
The Chemi.rtrjvo f the Hydrazo, Azo arid Azo.ry Groups (two ports)
The Cheniistry of Cyatintes arid their Thio Derivatives (two parts)
The Clicniistr:\~o f Dinzoniuni arid Diazo Groups (two parts)
The Chemistry of the Ccirbon-Cnrbon Triple Bond (two pcrrts)
Sirpplemerit A: The Chemistry of Double-bonded Functional Grolips (ttvo parts)
Preface to the series xi
The Chemistry of Ketenes, Allenes and Related Compounds (hvo parts)
Supplement B: The Chemistry of Acid Derivatives (two parts)
Supplement C: The Chemistry of Triple-Bonded Groups (two parts)
Supplement D: The Chemistry of Halides, Pseudo-halides and Azides (two parts)
Supplemgnt E: The Chetnistry of Ethers, Crown Ethers, Hydroxyl Groups arid their
Sulphur Analogues (two parts)
The Chetnistry of the Sulphoniuni Group (two parts)
Supplement F: The Chetnistry of Amino, Nitroso and Nitro Groups and their
Derivatives (two parts)
Titles in press:
The Chemistry of Peroxides
The Chemistry of Organometallic Compounds
The Chemistry of Organic Se and Te Compounds
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 Israel 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. Molecular mechanics and conformation 1
A. Meyer
2. Diamagnetic behaviour of compounds containing carbon-halogen bonds 49
R. R. Gupta
3. The mass spectra of azides and halides 75
J. M. Miller and T. R. B. Jones
4. Nuclear quadrupole resonance of carbon-bonded halogens 107
E. A. C. Lucken
5. 1,2-DehaIogenations and related reactions 161
E. Baciocchi
6. Electrochemical oxidation, reduction and formation of the C-X bond -
direct and indirect processes 203
J. Becker
Y.
7. Pyrolysis of aryl azides 287
L. K. Dyall
8. Vinyl, aryl and acyl azides 321
H. W. Moore and D. M. Goldish
9. Recent advances in the radiation chemistry of halocarbons 369
A. Horowitz
10. Organic chemistry of astatine 405
K. Berei and L. VasSros
11. Positive halogen compounds 44 1
A. Foucaud
12. Aspects of the Chemistry of halophenols and halodienones 481
J. M. Brittain and P. B. D. de la Mare
13. a-Halogenated imines 549
N. De Kimpe and R. VerhC
14. Fluorocarbons 603
B. E. Smart
15. Xenon halide halogenations 657
M. Zupan
16. The SRN1r eaction of organic halides 681
K. Norris
R.
...
XI11
xiv Contents
17. Reactions involving solid organic halides 703
E. Hadjoudis
18. Hypervalent halogen compounds 721
G. F. Koser
19. Synthesis and reactivity of a-halogenated ketones 81 3
R. VerhC and N. De Kimpe
20. Electrophilic assistance to reactions at a C-X bond 933
D. N. Kevill
21. Molecular interactions involving organic halides 985
J.-M. Dumas, M. Gomel and M. Guerin
22. Formation of carbon-halogen bonds 1021
M. Hudlicky and T. Hudlicky
23. Alkene-forming eliminations involving the carbon-halogen bond 1173
E. Baciocchi
24. Structural chemistry of the carbon-halogen and carbon-pseudohalogen
bonds 1229
M. Kaftory
25. Halonium ions 1265
G. F. Koser
26. Carbon-carbon bond formation involving organic halides and transition
metal compounds 1353
F. Naso and G. Marchese
27. Dihalocyclopropanes 1451
P. Weyerstahl
28. Photoelectron spectra of organic halogen compounds 1499
K. Wittel and H. Bock
29. Recent advances in the photochemistry of the carbon-halogen bond 1605
G. Lodder
Author Index 1685
Subject Index 1815