Double-Bonded Functional Groups: Volume 1 (1977)

659 Pages·1977·13.133 MB·English

Supplentent A The Chentistry 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
double- bonded
functional groups
Part 1
Edited h!.
SAULP ATAI
The Hrhre\j. Unii~ersitjJ~e,r usalem
1977
JOHN WILEY & SONS
LONDON--NEW YORK--SYDNEY--TORONTO
At1 Interscience @ Publication
Copyright 0 1977. by John Wilcy gL Sons. Ltd.
All rights reserved.
No part of this book may be reproduced by any means, nor
translated. nor transmitted into a machine language without
the written permission of the publisher.
Library of Congress C:italog Card No. 75-69 I -;.
ISBN 0 471 99463 2 (PI I).
ISBN 0 471 99465 0 (Pt 3).
ISBN 0 471 66940 7 (Set).
Produced in Great Britain by Technical Filmsetters Europe Ltd.
76 Great Bridgewater Street, Manchester MI
SJY.
Printed in Great Britain by Unwin Brothers Limited. The
Greshnm Press. Old Woking. Surrey.
TO
my grand-daughter Tat and the
double-bond between us
Contributing Authors
N. R. Barot Cheniistry Department, University of Nairobi,
Kenya
K. 6. Becker Institute of Organic Chemistry, University of Basel,
Switzerland
G. Bianchi Institute of Organic Chemistry, University of
Pavia, Italy
N. Calderon The Goodyear Tire & Rubber Co., Akron, Ohio,
U.S.A.
A. F. Cockerill Lilly Research Centre Ltd. Erl Wood Manor,
Windlesham, Surrey. U.K.
C. De Micheli 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 Wesleyan University, Middletown. Connecticut,
U.S.A.
R. Gandolfi Institute of Organic Chemistry, University of
Pavia, Italy
D. G. Garratt Department of Chemistry, University of Toronto,
Toronto, Ontario. Canada
C. A. Grob Institute of Organic Chemistry. University of Basel,
Switzerland
R. G. Harrison Lilly Research Centre Ltd. Erl Wood Manor,
Windleshani, Surrey, U.K.
P. M Henry Department of Chemistry, University of Guelph,
Guelph, Ontario, Canada
D. E. JanBes University of Iowa, Iowa City, Iowa. U.S.A.
G. Lange Department of Chemistry, University of Guelph,
L.
Guelph. Ontario. Canada
A. P. Marchand Department ofCliemistry. University ofOklahoma,
Norman. Oklahoma, U.S.A.
R. G. Reed The Mary Imogene Bassett Hospital, Cooperstown,
New York, U.S.A.
G. H. Schmid Department of Chemistry, University of Toronto,
Toronto, Ontario, Canada
vii
...
Vlll Contributing Authors
Shaw Physical Sciences Division, Stanford Research
R.
Institute, Menlo Park, California, U.S.A.
J. Stille University of Iowa, Iowa City, Iowa, U.S A.
K.
J. Van Meter Eastman Kodak Company, Rochester, f i w Y ork,
P.
U.S.A.
Foreword
Most of the originally planned volunies of the series The Cheriii.srry qf rhe
Firiicriorinl Gror~phs ave appeared already or are in the press. The first two
books of the series, Tho Cheriiisrrj: qfAlkerie.7 (1964) and The Cheiiiisrr>Jo f
rhe CarboiiTl Group (1966) each had ii second volume published in 1970,
with chapters not included in the plans of the original volumes and others
which were planned @ut failed to materialize.
This book is the first of a set of supplementary volumes which should
include material 011 more than a single functional group. For these volumes
a division into five categories is envisaged, and supplementary volumes in
e
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 :
Sirppieiiienr A : The Cheniistry of Double-Bonded Functional Groups
(C=C: C=O : C=N : N=N etc.).
Szrppleriierit B: The Chemistry of Acid Derivatives (COOH : COOR ;
CONHz etc.).
Sirppleiiierir C: The Chemistry of Triple-Bonded Functional Groups
+
(C-C; C-N; - N r N etc.).
Sirppleiiieiii D: The Chemistry of Hal@s and Pseudohalides (-F: -Cl;
-Br; -1: -N3: -0CN: -NCO etc.).
Sirppleiiienr E; Will include material on groups which do not fit any of
the previous four categories (-NH, -OH: -SH;
E
-NO2 etc.).
the present volume, as usual. the authors have been asked to write
In
chapters in the nature of essay-reviews not necessarily g;ving 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 PATAI
is
The @&emistry of Functional &-oups
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 Cheniistr)~ the Ether Lidicige deals with reactions in which
of
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 ;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 not to give an encj$opaedic
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 complere coverage of the subject with 110 overlap
between chapters, while at the same time preserving the readability of the
text. The Editor set himself the goal of attaining recisoiirihle coverage
with rnoriercite 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.
xi
xii Preface to the series
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 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 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 Chemistry of the Carhonjd Group, and a
chapter on ‘Ketenes’ is Jqcluded in the volume The Cheiiiisrry of’ Alkeiies).
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. ‘Polyethers’ in The Cheiiiisrrj~o f the Ether.
Liiikage, or ‘Tetraaminoethylenes’ in The Clteiiiisrr!~o fthe Aiiziiio 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 unevdn. Moreover.
a serious problem is caused by authors who deliver their manuscript late
or not at all. fn 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 develop-
ments in the sub-ject.s ufficient 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 Xlll
The overall plan of the volumes in the series 'The Chemistry of
Functional Groups' includes the titles listed below :
The C/ier~ii.stroj~f' Alkeries (publishetl in two voliiiiies)
The Chemistry of the Carboriyl Group (pirhli.sherl in two uolirriies)
The Chervisrry sf the Ether. Lirikage (pirblisherl)
The Cheriiistry ol'the Ai~iiioG roirp (publislietl)
Tlie Chemistry oftlie Nitro arid rlw Nitroso Group (puhlishetl in two purrs)
The Chemistry Of CarDosylic Acids arid Esters (piihlished)
The Clieiiiistrj, of the Carboii-Nitrogeii Double Borid (pirhlishen)
The Chemistry qf the Cyario Groirp (prrblidied)
The Clieiiiisrrj) of Aiiiides (pirblished)
The Cliemistry oj'tlie Hj?rli.osjd GI-oirp (pirhlishetl in two parts)
The Cher~iistryo f the Azido Groirp (pirhli.sher1)
Tlw Cliei?iistrj*o f Aq:l Halides (puhlishetl)
The Clieriiistrj~o J'tlie Carboii-Hologeii Bond (pirblislied iii titsop arts)
The Clier~iistr~ofy the Qiiirio~ioidC oriipoitiids (pi,hlis/ietii ri two par.~.~)
The CIieniistrI~o f the Tho1 Group (publislierl in two pcirts)
Tlie Cheriiisrry of' the Ctir~bori-Car*boriT riple Borirl (in pr.eparatiori)
The Cli er ii ist ry of Att i iditi es ~iid/in i dates @irblishen)
The Cheniist~yo f the Hjdrtrzo, Azo arid Azosjp Groups (pirblisketl)
The Ckerni,str-.j;o ftlie Cyaiiates trritl their Thio-derivatives (it1 ~WSS)
Tlie Cheiiiisrrj~o f the Di~i~oriiiirairi id Ditizo Groups (in press)
The Cheriiistr~lo f Citr~iuleriesa rid Heter~octrriiir1erie.s
Srrppleiiieiit A : The Clieniisrrj~ of' Doirhlc+ Borirled Firrictioiicil Groir ps
(published iri two prir-ts)
Sirpplement B : The Clier~iistr~oyf' Acid Derivariws (iri pr~par-ciriori)
Siippleriieiit C : Tlie Cheinistry of' Tsiple-Boiidcd Furic*tioiinlaG roups
S~ippleiiieiitD : The Clieriiisfry of H~1ide.st irid Pseudo-hcrlides
Strppleriierit E: Other Fiiiictioricil Gr*orrps
Advice or criticism regarding the plan arid execution of this series will
be welcomed by the Editor.
The publication of this series would nev!? have started, let alone con-
tinued, 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 invaluakk aid (but unfortunately their code of etbh
does not allow me to thank them by name). Many of my friends and
colleagues in Israel and overseas helped me in the solutio5 of various
major and niinor matters. and my thanks are due to all of them, especially
to Professor Z. Rappoport. Carrying out such a 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