Table Of ContentSynthesis of carboxylic acids, esters and their
derivatives
THE CHEMISTRY OF FUNCTIONAL GROUPS
A series ofadvanced treatises under the general editorship of Professor Saul Patai
The chemistry of alkenes (2 volumes)
The chemistry of the carbonyl group (2 volumes)
The chemistry of the ether linkage
The chemistry of the amino group
The chemistry of the nitro and nitroso groups (2 parts)
The chemistry of carboxylic acids and esters
The chemistry of the carbon-nitrogen double bond
The chemistry of amides
The chemistry of the cyano group
The chemistry of the hydroxyl group (2 parts)
The chemistry of the azido group
The chemistry of acyl halides
The chemistry of the carbon-halogen bond (2 parts)
The chemistry of the quinonoid compounds (2 volumes 4 parts)
The chemistry of the thiol group (2 parts)
The chemistry of the hydrazo azo and azoxy groups (2 parts)
The chemistry of amidines and imidates (2 volumes)
The chemistry of cyanates and their thio derivatives (2 parts)
The chemistry of diazonium and diazo groups (2 parts)
The chemistry of the carbon-carbon triple bond (2 parts)
The chemistry of ketenes, allenes and related compounds (2 parts)
The chemistry of the sulphonium group (2 parts)
Supplement A The chemistry of double-bonded functional groups (2 volumes 4 parts)
Supplement B The chemistry of acid derivatives (2 parts)
Supplement C The chemistry of triple-bonded functional groups (2 parts)
Supplement D The chemistry of halides, pseudo-halides and azides (2 parts)
Supplement E The chemistry of ethers crown ethers hydroxyl groups
and their sulphur analogues (2 parts)
Supplement F The chemistry of amino, nitroso and nitro compounds
and their derivatives (2 parts)
The chemistry of the metal-carbon bond (5 volumes)
The chemistry of peroxides
The chemistry of organic selenium and tellurium compounds (2 volumes)
The chemistry of the cyclopropyl group
The chemistry of organic silicon compounds (2 parts)
The chemistry of enones (2 parts)
The chemistry of sulphinic acids esters and their derivatives
The chemistry of sulphenic acids and their derivatives
The chemistry of organophosphorus compounds
The chemistry of enols
The chemistry of sulphonic acids esters and their derivatives
UPDATES
The chemistry of a-haloketones a-haloaldehydes and a haloimines
Nitrones nitronates and nitroxides
Crown ethers and analogs
Cyclopropane derived reactive intermediates
Synthesis of carboxylic acids esters and their derivatives
Patai s guide to the chemistry of functional groups-Saul Para/
Synthesis of carboxylic acids,
esters and their derivatives
MICHAEAL. OGLIARUSO
and
JAMESF . WOLFE
Virginia Polytechnic Institute and State University
Edited by
SAULP ATAaI nd ZVIR APPOPORT
The Hebrew University of Jerusalem
Updates from the Chemistry of Functional Groups
1991
JOHN WILEY & SONS
CHICHESTER . NEW YORK . BRISBANE . TORONTO. SINGAPORE
An Intersciences Publication
Copyright 0 1991 by John Wiley & Sons Ltd
Baffins Lane, Chichester, West Sussex PO19 IUD, England
All rights reserved
No part of this book may be reproduced by any means, or
transmitted, or translated into a machine language
without the written permission of the publisher
Other Wiley Editorial Offices
John Wiley & Sons, Inc., 605 Third Avenue,
New York, NY 10158-0012, USA
Jacaranda Wiley Ltd, G.P.O. Box 859, Brisbane,
Queensland 4001, Australia
John Wiley & Sons (Canada) Ltd, 22 Worcester Road,
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John Wiley & Sons (SEA) Pte Ltd, 37 Jalan Pemimpin 05-04,
Block B, Union Industrial Building, Singapore 2057
Library of Congress Cataloging-in-Publication Data:
Wolfe, James F.
Synthesis of carboxylic acids, esters, and their derivatives / by
Michael A. Ogliaruso, James F. Wolfe ; edited by Saul Patai and Zvi
Rappoport.
p. cm.-(The Chemistry of functional groups)
‘An Interscience publication.’
Includes bibliographical references and index.
ISBNO 471 91717 6
I. Carboxylic acids. 2. Esters. 3. Organic compounds-Synthesis.
I. Wolfe, James F. 11. Patai, Saul. 111. Rappoport, Zvi.
IV. Title. V. Series.
QD305A2W84 1991 90-43886
547‘.037-d~20 CIP
British Library Cataloguing in Publication Data:
Ogliaruso, Michael A.
Synthesis of carboxylic acids, esters and their
derivatives.
1. Carboxylic acids. Derivatives 2. Esters. Derivatives
1. Title 11. Wolfe, James F. 111. Patai, Saul IV.
Rappoport, Zvi V. Series
547.037
ISBNO 471 91717 6
Typeset by Thomson Press (India) Ltd, New Delhi, India.
Printed in Great Britain by Courier International Ltd, Tiptree, Essex
List of contributors
M. A. Ogliaruso Department of Chemistry, College of Arts and Sciences,
Virginia Polytechnic Institute and State University,
Blacksburg, Virginia 24061 -0699, USA
J. F. Wolfe Department of Chemistry, College of Arts and Sciences,
Virginia Polytechnic Institute and State University,
Blacksburg, Virginia 24061-0699, USA
V
This is the fifth volume in the new series entitled ‘Updates from the Chemistry of
Functional Groups’.
The volume contains the chapter by Professors M. A. Ogliaruso and J. F. Wolfe entitled
‘The synthesis ofcarboxylic acids and esters and their derivatives’as it appeared in 1979 in
‘Supplement B. The chemistry ofacid derivatives’. It is typical of the rapid development of
this subject that the ‘Appendix’ written by the same authors is almost twice as large as the
original chapter, although only a decade passed between the preparation of the two.
We will appreciate comments and suggestions regarding the present volume as bell as
other volumes of the main series or their updates.
Jerusalem SAULP ATAI
January 1991 ZVI RAPPOPORT
vii
Preface
Carboxylic acids, esters and their derivatives occupy a central position in the chemistry of
naturally occurring and synthetic organic compounds. Consequently, methods for the
synthesis and interconversions of these functional groups are of prime importance to
essentially every practicing organic chemist at one time or another. In view of this, and in
order to provide the series, The chemistry of Functional Groups, with a single source of
information on general methods for the synthesis of carboxylic acids, esters, acid
anhydrides, acyl halides, amides and imides, we authored a chapter on the synthesis of
carboxylic acids and their derivatives, which appeared in Suppkment B: The chemistry of
acid deriwtives. Purr I, pp. 267-490. That chapter contained descriptions of the most
common methods for the synthesis of acids and acid derivatives, with emphasis on
preparative techniques that appeared in the primary literature during the period, I967
through early 1976.
The present monograph volume on the synthesis of carboxylic acids and acid
derivatives represents our response to an invitation by the Editors and publishers of the
‘Functional Groups’ series of books to combine the material contained in the original
chapter with new methodology from the literature for the period, 1976 through 1987. The
format for this combination consists ofthe original text as published in 1979, along with an
up-to-date Appendix containing the newer material in the same format as used earlier.
This monograph is designed for the practicing chemist who seeks a convenient, single
source for synthetic methods leading to carboxylic acids and their derivatives. We have
attempted to include sufficient detail and examples of typical preparation to allow the
reader to make a rational choice from among several alternative methods. We realize that
there are certain to be synthetic procedures that we have failed to include, or have given
only cursory attention. For this, we apologize, with the sincere hope that what has heen
included will be of help and interest to our colleagues in the international organic
chemistry community.
We wish to express our gratitude to the Department of Chemistry at Virginia
Polytechnic Institute, which has been our professional home for a combined time of nearly
half-a-century. To the National Science Foundation, the National Institutes of Health,
and the Defense Advanced Research Project Administration, we extend our sincere
appreciation for financial support of our research efforts while this monograph was being
written. Finally, we thank Marion Bradley Via, without whose generosity this project
would have been impossible.
Blacksburg, MICHAEAL. OGLIARUSO
Virginia JAMISF . WOLFF.
1991
ix
Contents
1. The synthesis of carboxylic acids and esters and their derivatives 1
M. A. Ogliaruso and J. F. Wolfe
2. Appendix to 'The sy_nthesis of carboxylic acids and esters and their derivatives'
M. A. Ogliaruso and J. F. Wolfe 225
Author index 629
Subject index 671
xi
Synthesis of’carboxylic acids, esters and their derivatives
Edited by Saul Patai and Zvi Rappoport
Copyright 0 1991 by John Wiley & Sons Ltd
CHAPTER 1
The synthesis of
carboxylic acids and
esters and their derivatives
1. INTRODUCTION . .
4
11. SYNTHESIS CARBOXYLIC ACIDS . .
OF 4
A. Acids by Hydrolysis Reactions 5
1. Hydrolysis of esters . . 5
2. Hydrolysis of nitriles . 7
3. Hydrolysis of amides . 8
4. Hydrolysis of acyl halides and anhydrides . 9
5. Hydrolysis of trihalides . 9
6. Hydrolysis of dihalides . 10
B. Acids by Condensation Reactions . 10
1. Perkin reaction . 10
2. Doebner reaction . 11
3. Stobbe condensation . 11
4. Darzens condensation . 11
5. Wittig-type reactions . 12
6. Acetoacetic ester synthesis . 13
7. Malonic ester synthesis . 13
8. From dianions (&-anions) of carboxylic acids . 14
9. Michael reactions and related conjugate additions 16
10. Claisen condensation . 17
11. From oxazolines . 17
12. Coupling reactions . . 20
13. Miscellaneous condensation reactions . 21
a. Carbanion reactions . 21
b. From enamines . 22
C. Acids by Free-radical Processes . 22
1. Radical additions to unsaturated systems . 22
2. Carboxyalkylation of aromatic compounds . 23
D. Acids by Hydrocarboxylation Reactions . 24
E. Acids by Carbonation of Organometallic Reagents . 27
F. Acids by Electrophilic Substitution Reactions . 30
G. Acids by Oxidation Reactions . . 31
1. Oxidation of alcohols . 32
a. With base. . 32
b. With hypochlorite . 32
2 Michael A. Ogliaruso and James F. Wolfe
c. With oxides of chromium . . 32
d. With periodic acid and periodates . . 34
e. With oxides of manganese . . 35
f. With oxides of nitrogen . 37
g. With other oxides of metals . . 37
h. With air, oxygen and/or peroxides . . 39
i. With miscellaneous reagents . . 4 0
2. Oxidation of aldehydes . . 4 0
ab.. WWiitthh bcearsiec. i on . .. 4430
c. With oxides of chromium . . 43
.
d. With periodic acid and periodates . 4 4
fe.. WWiitthh ooxxiiddeess ooff mniatrnoggaenne se . .. 4474
g. With air, oxygen, acidified water and ozone . . 47
h. With oxides of selenium . 4;8;
i. With oxides of silver . .
j. With miscellaneous reagents .
3. Oxidation of arenes . . 51
a. With oxides of chromium . . 51
b. With periodic acid and periodates . . 53
c. With oxides of manganese . . 53
d. With oxides of nitrogen . 55
.
e. With sulphur compounds . 57
f. With oxides of selenium . 59
g. With other oxides of metals . . 59
.
h. With air, oxygen, peroxide and/or ozone . 6 0
i. With miscellaneous reagents . . 65
4. Oxidation of double and triple bonds . . 65
a. With base. . . 65
b. With oxides of chromium . . 65
c. With Lemieux-von Rudloff reagent . . . 66
d. With oxides of manganese . . 67
e. With oxides of nitrogen . 68
f. With oxides of ruthenium . . 69
g. With periodate, peroxyacids and ozone . . 70
h. With miscellaneous reagents . . 75
5. Oxidation of ethers, acetals and ketals . . 78
a. With boron fluorides . . 78
b. With acids . 79
c. With oxides of chromium . . 80
d. With ozone, peracids and peroxides . . 80
e. With trichloroisocyanuric acid . . 82
. .
f. With inorganic and organic halides 83
g. With miscellaneous reagents . . 85
6. Oxidation of ketones . . 87
a. With peracids (Baeyer-Villiger reaction) . . 81
b. With base. . 89
c. With ceric ammonium nitrate . . 92
d. With nitric acid . . 92
e. With alkali and halogen (haloform reaction) . . 92
f. With iodine-pyridine and alkali . . 95
g. With oxygen, ozone, peroxide or air . . . 95
h. With periodate . . 99
i. With light (photochemically) . . . 103
j. With sulphur (Willgerodt reaction) . . 103
With miscellaneous reagents . . 103
k.
