Double-Bonded Functional Groups: Volume 2 (1977)

700 Pages·1977·9.152 MB·English

Supplement A The Chemistry of Double-Bonded Functional Groups
Edited by Saul Patai
Copyright 0 1977. by John Wiley & Sons. Ltd. All rights reserved.
Supplement A
The chemistry of
Part 2
1977
JOHN WILEY & SONS
LONDON--NEW YORK--SYDNEY--TORONTO
Aii Iiircrscieiicc @ Piibliccirioii
Copyright 0 1977. by John Wiley gL Sons. Ltd.
All rights reserved.
No part of this book may be reproduced $y any means, nor
translated, nor transmitted into a machine language without
the written permission of the publisher.
Library of Congress Catalog Card No. 75-6913.
ISBN 0 471 99464 2 (Pt I).
ISBN 0 471 9Y465 0 (PI 2).
ISBN 0 471 66940 7 (Set).
Produced in Great Britain by Technical Filmsetters Europe Lid.
76 Great Bridgewater Street. Manchester M 1 5JY.
Printed in Great Britain by Unwin Brothers Liniired. The
Greshani Press. Old Woking. Surrey.
To
my grand-daughter Tal and the
double-bond between us
Contributing Authors
N. I?. Barot Chemistry Departnient, University of Nairobi,
Kenya
K. B. Becker Institute of Organic Chemistry, University of Basel,
Switzerland
G. Bianchi Institute of Organic Chemistry. University of
Pavia, Italy
N. Calderon The Goodyear Tire Br Rubber Co., Akron, Ohio.
U.S.A.
A. F. Cockerill Lilly Research Centre Ltd. Erl Wood Manor,
Windlesham. Surrey. U.K.
C. De Michelis Institute of Organic Chemistry, University of
Pavia. Italy
J. A. Elvidge Chemistry Department. University of Surrey. U.K.
0. Exner Institute of Organic Chemistry and Biochemistry.
Czechoslovak Academy of Science. Prague,
Czechoslovakia
A. J. Fry Wesley an U n i ve rsi t y , M idd I et o w n, Con necl icu t ,
U.S.A.
R. Gandolfi Institute of Oryriic Chemistry, University of
Pavia. Italy
D. G. Garratt Department of Chemistry. University of Toronto,
Toronto, Ontario, Canada
C. A. Grob Institute of Orsanic Chemistry, University of Basel,
Switzerland
R. G. Harrison Lilly Research Centre Ltd. Erl Wood Manor,
W i nd les ha in. Surrey. U .K .
P. M Henry Depart in en t o f C he ini s t r y , U n i ve rs i t p o f G lie rp 11,
# Guelph. Ontario, Canada
D. E. James University of Iowa. lowa City, lowa. U.S.A.
G. L. Lange Department of Chemistry, University of Guelph,
Guelph, Ontario. Canada
A. P. Marchand Department ofChemistry. University ofOklahoma,
Norman, 0 k I a 11 oma, U. S.A .
R. G. Reed The Mary 1m ogene Basset1 Hospital. Cooperstown,
New Yo& U.S.A.
G. H. Schmid Department of Chemistry. University of Toronto,
Toronto. Ontario. Canada
vi i
...
Vlll Contributing Authors
R. Shaw Physical Sciences Division, Stanford Research
Institute, Menlo Park, California, U.S.A.
J. K. Sti!le University oi Iowa, Iowa City, Iowa, U.S.A.
J. P. Van Meter Eastman Kodak Company, Rochester, New York,
U.S.A.
Foreword
Most of the originally planned volumes of the series The Chentistr.j~o f the
F~inctiurrdG roups have appeared already or are in the press. The first two
books of the series, The Chemistry uJAllceries (19 64) and The Chemistry of
the Curbmy1 Group (1966) each had a second volume published in 1970,
with chapters not included in the plans of the original volumes and others
which were planned but failed tc materialize.
This book is the first of a set of supplementary volumes which sliould
include material on more than a single functional group. For these volumes
a division into five categories is envisaged, and supplementary volumes in
each of these categories will be published as the need arises. These volumes
should include ‘missing chapters’ as well as chapters which give a unified
and comparative treatment of several related functional groups together.
The planned division is as follows:
Si/ppleriterir A : The Chemistry of Double-Bonded Functional Groups
(C=C: C=O : C=N ; N=N etc.).
Supplei~teittB : The Chemistry of Acid Derivatives (COOH : COOR :
CONHz etc.).
Siipplenienr C: The Chemistry of Triple-Bonded Functional Groups
+
(CEC; C=N I - N r N etc.).
Sirpplem~rtrD : The Chemistry of Halides and Pseudohalides (- F; -C1;
-Br; -1; -N3: -0CN; -NCO etc.).
Siipplentent €1 Will include material on groups which do not fit any of
the previous four categories (-NH, : -OH: -SH;
-NO, etc.).
Jii the present volume, as usual, the authors have been asked to write
chapters in the nature of essw-reviews not necessarily giving extensive or
encyclopaedic coverage of the material. Once more, not all planned
chapters materialized, but we hope that additional volumes of Supplement
A will appear. when these gaps can be filled together with coverage of
new developments in the various fields treated.
Jerusalem, March 1976 SAUL PATAl
IX
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
c
treated and on the effects which it exerts on tlie chemical and p!iysical
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 Cheniistr-y ofthe 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 tlie ether
c
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 no1 the whole molecule,
but tlie 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 ;is 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 iiot :o give an encyclopaedic
coverage of his subject, but to concentrate on tlie most important recent
developments and mainly on material that has not beg1 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 coiiiplete coverage of the subject with 110 overlap
between chapters, while at the same time preserving the readability of tlie
text. The Editor set himself tlie goal of attaining r*en.soiitrhle coverage
with iiiorler.cirr 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 cli*iiXcrs.
4
xi
xii Preface to the series
The general plan of each volume includes the following main sections :
(a) An introductory csapter dealing with the general and theoretical
aspects of the g e ~ p .
(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 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).
9
(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 reac-
tions. 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 Cheinistrjr ofthe Cu~*boiiyGl roup, and a
chapter on ‘Ketenes’ is included in the volume The Clieniisrrj- yf’A1kc.ne.s).
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. ‘Pol yethers’ in The C11eniisti.jo~f ’the Ether
Linkage, or ‘Tetraaminoethylenes’ in The Clieniistrj-o frlie Amiiio Group.
This plan entails that the breadth, depth and thought-provoking nature
of 2ach 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-deli- of chapters. or to new develop-
ments in the sub.ject. sufficient material has accumulated for publication of
a supplementary volume. containing material on related functional groups.
this will be done as soon as possible.
-
...
Preface to the series XI11
The overall plan of the volumes in tlie series 'The Chemistry of
Functional Groups' includes the titles listed below :
The Cheiiiistry of' Alkeiies (published iii two uolcriiies)
The Chemistry of the Curhoiiyl Group (pirblislied iri two ooliriiies)
The Cheiiiistr.jp of the Ether Liiikuge (pirbli.sherl)
The Cliei)iistry of' the Aniiiio Grocrp (publislied)
The Cheiiiistry of'the Nitro tml the Nitroso Groirp (pirblished iii t\vo pcrrts)
The Cliernistrj~o f Cai-bosjllic Acids aiid Esters (prrhlished)
The Cheniistry of' [lie C(irboii-Niti.ogen Doirble Botid (pirblislied)
Tlie Cheiiii.strjpo f' the Cjaiio Groirp (prrblishetl)
The Cheiiiistry of Aiiiides (pirblished)
The Cheiiiisrr.jp oftlie Hj)dros!~Gl roirp (pirhlisltetl iii t\vo parts)
The C1ieiiiistr.j~o f the Azido Group (pirhlisherl)
The Clieniistrj. qf Aqd Hrr1itie.r (pirblishecl)
The CIieniistrj3o f the Cnrbon-Hnlogeii Boiid (piiblished in tu'o parts)
.r;l Tlie Cheiiiistrj?o fthe Qrtiriorioid Coiiipoirrrtls (pctblisherl iii two parts)
The Clieriiistrj~y /' the Thiol GI-oiip (puhlisheci' iii two purts)
The C1ieiiii.sti.y olf'tlie Cni-boii-Carboii Triple Boiitl (in preparcitioit)
The Clieniistry of' Amidines and linidates (published)
Tlie Cheiiiistrjl of' the H.wlrlir-.o,A zo ciiitl Azosji Groirps (pirhlislierl)
The Cheiiiisrry OJ'the Cjy1iicite.s ciiirl tlieii. Tliio-rler;iucitii!rs (iii pi.e.s.s)
The Clientistry of' the Dinzoniirni nriil Dinzo Groups (in pi-ess)
Tlie CI1eiiiistr.v of' Ciriiiirleiies and Hc~teroc~eriiirrleries
Sirppleiiierit A : The Clieiiiistrj. qf' Double-Boiirlrtl Firrictioiirrl Gro1rp.s
(published iii two pnrts)
Suppleiiieiit B : The Cheiiiistrji of Acid Deriiintiix..~( iii prepciiwtioii)
Srippleiiienr C : The Cheiiiistry of TripIe-Boiidi~dF iriictioiinl Groups
Sirppleiiieiit D : The Clieiiiistr!~o f' Holitles niid Psetrtlo-1icilidi.s
Sirppleiiiiwt E : Other. Fitiictioiicil Gi-oirps
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 con-
tinued, without tlie 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 stafl-members of the Publisher
also rendered me invaluable aid (but unfo~-tunatelyt heir 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 diie to all of them. especially
to Professor Z. Rappoport. Carrying out such ii long-range project would
xiv Preface to the series
be quite impossible without the non-professional but none the less essential
participation and partnership of my wife.
The Hebrew University, SAULP ATAI
Jerusalem, ISRAEL