Table Of ContentThe Chemistry of the Sulphonium Group
Edited by C. J. M. Stirling and S. Patai
@ 1981 John Wiley & Sons Ltd.
The chemistry of the
a
s
Part 1
Edited by
C. M. STIRLING
J.
School of Physical and Molecular Sciences
University College of North Wales
Bangor
1981
JOHN WILEY & SONS
CHICHESTER - NEW YORK - BRISBANE -TORONTO
A ii In re rsc ienc e 6 Public n t io 11
Copyright 0 1981 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.
British Library Cataloguing in Publication Data:
The chemistry of the sulphonium group.-(The
chemistry of functional groups).
Part i
I. Sulphonium compounds
1. Stirling. Charles James Matthew
11. Series
547’.065 QD34 1 .S8 80-401 22
ISBN 0 471 27769 X
ISBN 0 471 27655 3 Set of 2 vols
Typeset by Preface Ltd. Salisbury Wilts.
Printed in the United States of America.
FOR E. AND L.-
ANOTHER LINK BETWEEN WALES AND ISRAEL
h m v 7 1 05711 772 xqx~i, .'?, .K T I ~ Y;'r m~pa
CYSWLLT ARALL RHWNG CYMRU AC ISRAEL
Contributing authors
K. K. Andersen Department of Chemistry. University of New Hampshire.
Durham, New Hampshire 03824, USA
R. F. Ashworth Lehrstuhl fur Organische Analytik, Universitat des
M.
Saarlandes. Fachbereich 66 Saarbrucken. W. Germany
15.3.
G. C. Barrett Oxford Polytechnic, Headington, Oxford OX3 OBP, England
L. F. Blackwell Department of Chemistry, Biochemistry and Biophysics.
Massey University, Palmerston North, New Zealand
E. Block Department of Chemistry, University of Missouri-St. Louis,
St. Louis. Missouri 63121, USA
J. D. Coyle Chemistry Department. The Open University, Milton Keynes
MK7 6AA. England
D. C. Dittmer Department of Chemistry. Syracuse University, Syracuse. New
York 13210. USA
A. Gavezzotti Istituto di Chimica Fisica e Centro CNR. Universita di Milano.
Milan. Italy
J. Grimshaw Department of Chemistry. David Keir Building, Queen’s
University of Belfast. Belfast BT9 5AG, N. Ireland
A. C. Knipe School of Physical Sciences. The New University of Ulster.
Coleraine. Co. Londonderry, Northern Ireland 3T42 1S A
P. A. Lowe The Ramage Laboratories. Department of Chemistry and
Applied Chemistry. University of Salford. Salford 4WT.
M5
England
G. A. Maw Department of Biochemistry, Glasshouse Crops Research
Institute. Littleharnpton. Sussex. England
T. Numata Department of Chemistry. University of Tsukuba.
Sakura-rnura, Ibaraki, 305 Japan
S. Oae Department- of Chemistry. University of Tsukuba.
Sakura-mura, Ibaraki, 305 Japan
B. Patwardhan Department of Chemistry. Syracuse University. Syracuse. New
H.
York 13210. USA
I. C. Paul Department of Chemistry. School of Chemical Sciences.
University of Illinois. Urbana. Illinois 6 180 1. USA
vii
...
Vlll Conrribirritig authors
E. F. Perozzi Ethyl Corporation. 1600 West Eight Mile Road, Ferndale,
Michigan 48220, U.S.A.
R. Shaw Chemistry Department. Lockheed Palo Alto Research
Laboratory. Lockheed Missiles & Space Company, Inc., 3251
Hanover Street. Palo Alto. California 94304, USA
H. J. Shine Department of Chemistry. Texas Tech University. Lubbock,
Texas 79409. USA
J. Shorter Department of Chemistry. The University, Hull HU6 7RX.
England
M. Simonetta Istituto di Chimica Fisica e Centro CNR, Universiti di Milano,
Milan. Italy
T. Yoshimura Department of Chemistry, University of Tsukuba,
Sakura-mura, Ibaraki, 305 Japan
Foreword
Our collaboration on production of this volume the chemistry of the
on
sulphonium group arose from a sabbatical visit from Wales to Israel.
There is remarkably little review literature on the chemistry of this group, one of
the most versatile in organic chemistry, and we have been most fortunate in the
group of contributors who have brought this volume to fruition. Chapters on
nuclear magnetic resonance spectroscopy and mass spectroscopy did not materialise
in time for publication.
We hope that assembly of so much up to date information on this functional
group will stimulate further exploration of its wide-ranging and fascinating
chemistry.
The preface to the series contains the promise of further volumes on the
chemistry of sulphur-containing compounds. We are in the early stages of planning
further volumes in the series on the chemistry of other sulphur-containing
functional groups, notably those concerned with sulphonyl and sulphinyl groups.
Bangor CHARLES STIRLING
May 1980
Jerusalem SAUL PATAI
ix
The Chemistry ~d Functionall 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 rhe Erher 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 nor 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 complerc coverage of the subject with no overlap between
chapters. while at the same time preserving the readability of the text. The Editor
set himself the goal of attaining rcwsotinblc coverage with rizodernrc 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.
x
Preface to the series xi
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 method of
determination including chemical and physical 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 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
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 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). other cases certain compounds. though
In
containing only the functional group of the title. may have special features so as to
be best tieated in a separate chapter, as e.g. ‘Polyethers’ in The Chemistry of the
Ether Linkage, or ‘Tetraaminoethylenes’ in The Chetnistry 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:
Tlic Chrmistry of Alketies (IH~Ov olumes)
Thc. Chemistry of the Carbonyl Groirp (~M‘vool irmcs)
The Chemistry of thc Ether_ Linkage
The Clirmistry of the Amino Group
Tlir Ciicvnistry of thc Nitro arid Nitroso Groirps (t1t-op arts)
Tlic C’lictnistry of Carboxylic Acids arid Esters
Tlic Chemistry of tlic Carbon-Nitrogcti Doirblp Bond
Tlic Ciiivnistry of thr Cynno Group
Thii Cliivtiistry of Atnidt.s
Thi, Cliiwiistry of tlic Hdrosyl Group (11c.0 parts)
Tlic Clictnistry of tlic Azidii Group
xii Preface to the series
The Chemistry of Acyl Halides
The Chemistry of the Carbon-Halogen Bond (tlz’o parts)
The Chemistry of Quinonoid Compounds (two parts)
The Chemistry of the Thiol Group (two parts)
The Chemistry of Amidines and Itnidates
The Chemistry of the Hydrazo, Azo and Azoxy Groups
The Chemistry of Cyanates and their Thio Derivatives (two parts)
The Chemistry of Diazonium and Diazo Groups (two parts)
The Chemistry of the Carbon-Carbon Triple Bond (two parts)
Supplement A: The Chetnistry of Double-bonded Functional Groups (two parts)
Supplement B: The Clientistry of Acid Derivatives (two parts)
The Chemistry of Ketenes, AIlenes and Related Compoutids (two parts)
The Chemistry of the Sulphonium Group (two parts)
Titles in press:
Supplement E: The Chemistry of Ethers, Crowti Ethers, Hydroxyl Groups
and their Sulphur Analogs
Future volumes planned include:
The Chemistry of Orgntiomctallic Compoutids
The Chemistry of Sulphur-coIitnitiitig Conlpounds
Supplement C: The Chemistry of Triple-bonded Functional Groups
Supplemetit D: The Cfietnistry of Hnlides and Pseudo-halides
Supplement F: The Chemistry of Atnines, Nitroso and Nitro Groups arid their
Derivatives
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 rxe 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
1. General and theoretical aspects 1
M. Simonetta and A. Gavezzotti
2. The structural chemistry of sulphonium salts 15
E. F. Perozzi and I. C. Paul
3. Analysis and determination 79
M. F. Ashworth
El.
4. Thermochemistry of the sulphonium group 101
R. Shaw
5. Photochemistry of sulphonium compounds 107
J. D. Coyle
6. Electronic spectra 123
G. C. Barrett
7. Electrochemistry of the sulphonium group 141
J. Grimshaw
8. Isotopically labelled sulphonium salts 157
L. F. Blackwell
9. Electronic effects of the sulphonium group 187
J. Shorter
10. Stereochemistry and chiroptical properties of the sulphonium group 229
K. K. Andersen
11. Synthesis of sulphonium salts 267
P. A. Lowe
12. Reactivity of sulphonium salts 313
A. C. Knipe
13. Cyclic sulphonium salts 387
D. C. Dittmer and B. H. Patwardhan
14. Organosulphur cation radicals 523
H. J. Shine
...
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