Carboxylic Acids and Esters (1969)

1157 Pages·1969·0.3 MB·English

The Chemistry of Curboxylic Acids and Esters
Edited by Saul Patai
Copyright 0 1969 by John Wiley & Sons Ltd. All rights reserved.
The
chemistry of
Edired by
SAUL PATAI
The Hebrew University
Jerusalem, Israel
1969
I ERSCl EN CE-PU BLlS HE R S
NY
a division Wiley & Sons Ltd.
of John
CHICHESTEK - NEW YORK - ljKlSBANE - TORONTO
First published by John Wiley & Ltd. 1969
Sons
All rights reserved. No part of this book may be
reproduced by means, nor transmitted,
any nor
translated into a machine language without the
written permksion the publisher.
of
Library Congress catalog card number 70-82547
of
ISBN 0 471 66919 9
Reprinted 1974
Reprinted 1979
Printed in Great Britain
Unwin Brothers Limited
by
The Gresham Press, Old Woking, Surrey,
A member of the Staples Printing Group
Contributing authors
I.D . Bergelson Institute for Chemistry of Natural Products,
Academy of Sciences of the U.S.S.R.,
Moscow, U.S.S.R.
Sergio Card Institute Chemical Physics, University
of of
Milan, Italy.
Louis W. Clark Western Carolina University, Cullowhee,
North Carolina, U.S.A.
E. Cordes I-n-d iana University, Bloomington, Indiana,
H.
U .1L A.
Shawn Doonan University College, London, England.
Len nart Eberson University Lund, Sweden.
of
Erkki K. Euranto University Turku, Finland.
of
Matthys j. janssen The University, Groningen, Netherlands.
Kenneth King University Delaware, Newark, Delaware,
of
U.S.A.
G. Kohnstam University of Durham, England.
Jouk o Kos kik al Ii o University of Oulu, Finland.
V. F. Kucherov N. D. Zelinsky Institute of Organic Chemis-
try, Academy of Sciences of the U.S.S.R.,
Moscow, U.S.S.R.
Harold Kwart University of Delaware, Newark, Delaware,
U.S.A.
Sven-Olov Lawesson University of Aarhus, Denmark.
T. S. Ma City University New York, U.S.A.
of
D. P. N. Satchell King’s College, London, England.
R. S. Satchell Queen Elizabeth College, London, England.
Gustav Schroll University of Aarhus, Denmark.
M. M. Shemyakin Institute for Chemistry of Natural Products,
Academy of Sciences the U.S.S.R.,
of
Moscow, U .S .S.R.
Massimo Simonetta Institute of Chemical Physics, University
of
Milan, Italy.
R. P. A. Sneeden Monsanto Research S.A., Zurich, Switzer-
land.
V
vi Contributing authors
L. H. Williams University of Durham, England.
D.
A. .Yanovskaya N. D. Zelhsky Institute of Organic Chemk-
L.
try, Academy of Sciences of the U.S.S.R.,
Moscow, U.S.S.R.
Mieczyslaw Zielinski University of Warsaw, Poland.
The principles governing the plan and pattern of the present volume have
been summarized in the Preface to the series ‘The Chemistry of Functional
Groups’.
Out of the originally planned contents, two chapters failed to material-
ize. These should have been chapters ‘Formation of COOH Groups’
on
and ‘Radiation and Photochemistry’.
SAULP AT&
Jerusalem, September 1968
The Chemistry of the Functional
Preface to the series
The series ‘The Chemistry of the Functional Groups’ is planned to cover
in each volume all aspects of the chemistry of one of the important finc-
tional groups in organic chemistry. The emphasis is laid on the functional
group treated and on the effects which it exerts on the chemical and physi-
cal 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 Linkage deals with reactions in
which the C-0--C groilp 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 cover-
age of all properties and reactions of ethers in far as these depend on
as
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 Re-
views, 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, a rule, be repeated
as
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 cover-
age of his subject, but to concentrate on the most important recent devel-
opments 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 adress 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 no overlap
between the chapters, while at the same time preserving the readability
of the text. The Editor set himself the goal of attaining reasonable coverage
with moderate overlap, with a minimum of cross-references between the
ix
X Preface to the Series
chapters of each volume. In this manner, sufficient freedom is given to
each author to produce readable quasimonographic 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 more chapters dealing with the formation of the functional
or
group in question, either from groups present in the molecule, or by intro-
ducing the new group directly indirectly.
or
(c) Chapters describing the characterjzation and characteristics of the
functional groups, i.e. a chapter dealing with qualitative and quantitative
methods of determination including chemical and physical methods, ultra-
violet, infrared, nuclear magnetic resonance, and mass spectra; a chapter
dealing with activating and directive effects exerted by the group and/or
a chapter the basicity, acidity complex-forming ability of the group
on or
(if applicable).
(d) Chapters on the reactions, tranformations and rearrangements
which the functional group can undergo, either alone or in conjunction
with other reagents.
(c) Special topics which do not fit any of the above sections, such as
photochemistry, radiation chemistry, biochemical formations and reac-
tions. Depending on the aature of each functional group treated, these
special topics may include short monographs on related functional groups
which no separate volume is planned (e.g. a chapter on ‘Thioketones’
on is
included in the volume The Chemistry of the Carbony2 Group, and a chapter
‘Ketenes’ is included in the volume The Chemistry of Alkenes). In other
on
cases, certain compounds, though containing only the functional group
of the title, may have special features so as to best treated in a separate
be
chapter e.g. ‘Polyethers’ in The Chemistry of the Ether Linkage, or
as
‘Tctraaminoethylenes’ in The Chemistry of the Amino Group.
This plan entails that the breadth, depth and thought-provoking nature
of chapter will differ with the views and inclinations of the author
each
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
Preface to the Series xi
consideration to the originally planned logical order of the chapters. If
after the appearance of the originally plenned parts a volume, it is
of
found that either owing to non-delivery of chapters, or to new develop-
ments in the subject, sufficieat material has accumulated for publication
an additional part, this wi!l be done as soon as possible.
of
It is hoped that future volumes in the series ‘The Chemistry of the
Functional Groups’ will include the topics listed below:
The Chemistry of the Alkenes (publ ished)
The Chemistry of the Carbonyl Group (published)
The Chemistry of the Ether Linkage (published)
The Chemistry of the -4mino Group (published)
The Chemistry of the Nitro and Nitroso Group (published)
The Chemistry of Carboxylic Acids and Esters (published)
The chemistry of the Carbon-Nitrogen Double Bond (in press)
TAe Cfiemistry of the Cyano Group (in press)
The Chemistry of the Amides (in press)
The Chemistry of the Carbon-Halogen Bond
The Chemistry of the Hydroxyl Group (in preparation)
The Chemistry of the Carbon-Cmbon Tr@leB ond
The Chemistry of the Azido Group (in preparation)
The Chemistry of Imidoates and Amidiim
The Chemistry if the Thiol Group
The Chemistry of the Hydrazo, Azo and Azoxy Groups
The Chemistry of Carbonyl Halides
The Chemistry of the SO,S On, --SO& and --S03H Groups
The Chemistry of the -OCN, -NCO and -SCN Groups
The Chemistry of the -POSH2 and Related Groups
Advice criticism regarding the plan and execution this series will
or of
be welcomed by the Editor.
The publication of this series would never 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 and who continues to help and advise me. The effi-
task,
cient and patient cooperation of several staE-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 friends and colleagues
my
in Jerusalem helped me in the solution of various major and minor matters
and thanks are due especially to Prof. Liwschitz, Dr. Z. Rappoport
my Y.
xii Preface to the Series
and Dr. J. Zabicky. Carrying out such a long-range project would be
quite impossible without the non-professional but none the less essential
participation and partaership of my wife.
The Hebrew University, SAULP ATAI
Jerusalem, ISRAEL
contents
General and theoretical aspects of the COOH and COOR groups
0.
Massirno Simonetta and Sergio Carrii 1
2. Electrochemical reactions of carboxylic acids and related processes
Lennart Eberson 53
3. Alcoholysis, acidolysis and redistribution of esters
Jouko Koskikallio 103
4. The formation of carboxylic acids and their derivatives from
organom eta II i c com poun ds
R. P. A. Sneeden 137
5. Synthesis of di- and polycarboxylic acids and esters
V. F. Kucherov and L. A. Yanovskaya 175
6. Acidity and hydrogen bonding of carboxyl groups
Lennart Eberson 21 1
7. Introduction of COOH groups by carbonyl olefination
L. D. Bergelson and M. M. Shemyakin 29 5
8. Rearrangement and cyclization reactions of carboxylic acids and
esters
Harold Kwart and Kenneth King 34 1
9. Substitution in the groups COOH and COOR
D. P. N. Satchell and R. S. Satchell 375
10. Syntheses and uses of isotopically labelled carboxylic acids
Mieczyslaw Zielinski 453
1;. Esterification and ester hydrolysis
Erkki K. Euranto 505
12. The decarboxylation reaction
Louis W. Clark 5 89
13. Ortho esters
E. H. Cordes
623
14. Peracids and peresters
Sven-Olov Lawesson and Gustav Schroll 669
15. Thiolo, thiono and dithio acids and esters
Matthys J. Janssen 705
...
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