The Carbonyl Group: Volume 1 (1966)

1027 Pages·1966·26.046 MB·English

The Chemistry of the Carbonyl Group
Edited by Saul Patai
Copyright 0 1966 by John Wiley & Sons Ltd. All rights reserved.
The chemistry of
Edited bp
SAUL PATAI
The Hebrew University
Jerusalem, Israel
1966
INTERSCIENCE PUBLISHERS
a division of John Wiley & Sons
CHICHESTER - NEW YORK - BRISBANE - TORONTO
Copyright @ 1966 by John Wiley & Sons Ltd.
All rights reserved. No part of this publication
may be reproduced, stored in a retrieval system,
or transmitted, in any form or by any means,
electronic, mechanical photocopying, recording
or otherwise, without the prior written per-
mission of the Copyright owner.
Library of Congress catalog card number 66-181 77
ISBN 0 470 66920 9
Reprinted I971
HeprinLed 1973
Reprinted 1979
Reproduced phofo-lilho in Great Britain by
J. I+'. Arrowstnith Ltd., Bristol 3.
The editor dedicates this volume, with humble thanks, to
Mr.
Donald Ross
who uses the resources of surgery and science and above
these his understanding and humanity in order to aid, to
restore, and to heal
Contributing authors
G. Berthier Centre National de la Recherche Scientifique,
Paris, France
?Aichael Cais T---1-.-: - . - israei institute of Technology,
I G;cIImvkL
Haifa, Israel
Campaigne Indiana University, U.S.A.
E.
Clair J. Collins Oak Ridge National Laboratory and The Uni-
versity of Tennessee, U.S.A.
C. F. Cullis Imperial College, London, England
Jerome Eastham University of Tennessee, U.S.A.
F.
Theophil Eicher University of Wiirzburg, Germany
Frank Eisenberg, Jr. National Institutes of Health, Bethesda, Mary-
land, U.S.A.
A. Fish Imperial Collegc, London, England
Reynold C. Fuson University of Ncvada, U.S.A.
U. L. Haldna Tartu State University, Estonian SSR, USSR
Gordon Hanna Olin Mathieson Chemical Corp., New Haven.
J.
Connecticut, U.S.A.
Robert Roy Kintner Augustana College, South Dakota, U.S.A.
Asher Mandelbaum Technion - Israel Institute of Technology,
Haifa, Israel
A. Palm Tartu State University, I3stonian SSR, USSR
V.
Pitts, Jr. Univcrsity of California, Riverside, U.S.A.
J. N:
Richard L. Reeves Eastman Kodak Company, Rochester, New
York, U.S.A.
Jan RoEek The Catholic University of America, Washing-
ton, U.S.A.
Pentti Salomaa University of Turku, Finland
D. Satchell King’s College, London, England
P. N.
R. S. Satchell Queen Elizabeth College, London, England
Vii
Contri but i aut rs-cod.
ng ho
W. M. Schubert University of Washington, U.S.A.
J. Serre $Cole SupCrieure, Paris, France
A. J. Talvik Tartu State University, Estonian USSR
SSR,
Wan University California, Riverside, U.S.A.
J. K. S. of
Owen H. Wheeler Puerto Rico Nuclear Center, Mayaguez, Puerto
Rico
viii
FQr eword
This book is the second in a series of treatises dealing with the chem-
istry of functional groups. As in the first volume (The Chemistry of
AIkmes, 1954), this present volume again attempts to encompass all
facets of a functional group and to give up-to-date descriptions of the
nature of the carbonyl group, of the main pathways leading to its
formation, and of its main modes of reaction. Special topics, such as
the biochemistry and the photochemistry of the carbonyl group and
the chemistry of thiocarbonyl compounds, are treated in separate
chapters.
The authors of the chapters were asked to concentrate their efforts
on a critical discussion of their subjects, emphasizing recent advances
and new developments, and addressing themselves mainly to post-
graduate students and research workers. Material appearing in
modern testbooks or reviewed satisfactorily in easily available
sources was to be covered briefly and only then if it was considered
to be necessary for the balance of the presentation. Nevertheless, each
author was asked to treat his subject monographically and a certain
amount of overlap between the chapters was accepted in order to
preserve their structural unity and to spare the reader from too fre-
quent recourse to different chapters of the book.
Two of the chapters promiscd for the book failed to materialize on
time (‘Equilibrium additions to carbonyl groups’ and ‘ Syntheses
and uses of isotopically labelled carbonyl compounds ’). The policy
previously established for the series was followed again and the
volume is presented on schedule, the editor and publisher preferring
relative incompleteness to obsolescence.
For the guidance and trust of Dr. Arnold M‘eissberger, my mentor
and friend, I continue to stand indebted. Most of my editorial work
on this volume was carried out in a period of hardship and calamity :
the shared strength and understanding of my wife made coniplction
of my task possible. I also wish to thank the staff of the publisher’s
editorial office in London for their exceptional patience, helpfulness,
and efficiency.
Jerusalem, November 1965 SAULP ATAI
ix
Contents
1. General and theoretical aspects of the carbonyl
group 1
G. Bert!iier 2nd J. Szrre
2. Car b o ny I-f o r m in g oxi d at io ns 79
C. F. Cullis and A. Fish
3. Formation of carbonyl groups in hydrolytic reac-
tions 177
Pentti Salomaa
4. Formation of aldehydes and ketones from carboxylic
acids and their derivatives 211
Reynold C. Fuson
5. Formation of ketones and aldehydes by acylation,
formylation and some related processes 233
D. P. N. Satchel1 and R. S. Satchel1
6. Carbonyl syntheses through organometallics
303
Michael Cais and Asher iMandelbaum
7. Biological formation and reactions of carbonyl
groups 33 1
Frank Eisenberg, Jr.
8, Chemical and physical methods of analysis 375
J. Gordon Hanna
9. Basicity of carbonyl compounds 42 1
V. A. Palm, 0.L . Haldna and A. J. Talvik
10. Oxidation of aldehydes by transition metals 46 1
Jan RoEek
11. Reduction of carbonyl groups 507
Owen H. Wheeler
12, Condensations leading to double bonds 567
Richard L. Reeves
13, Reactions of carbonyl groups with organometallic
compounds 62 1
Theophil Eicher
xi
xii Contents
Co nts-con t.
nte
14. Decarbonylation 695
W. M. Schubert and Robert Kintner
Roy
15. Rearrangements involving the carbonyl group 761
Clair J. Collins and Jerome F. Eastham
16. Photochemistry of ketones and aldehydes 823
J. N. Pitts, Jr., and J. K. S. Wan
17. Thioketones 917
E. Campaigne
Author index 96 1
Subject index 1011
The Chemistry of the Carbonyl Group
Edited by Saul Patai
Copyright 0 1966 by John Wiley & Sons Ltd. All rights reserved.
1
CHAPTER
G. BERTHIER
Centre National de la Recherche ScientiJque, Paris, France
and
J. SERRE
&ole Normale Supkieure, Paris, France
.
I. INTRODUCTION 2
11. PHYSICOCHEMPIICCTAULR OEF THE CARBONYGLR OUP. 3
.
A. Physical Properties and Polarity 3
.
1. Length of the -0 3
. bond
2. Bond energies 5
3. "uipoie moments . 6
4. Ionization potentials . 8
5. Vibration spectra . 11
B. Ultraviolet Spectra . 17
1. n+m* transitions 19
2. transitions 28
~?vrr*
3. Other transitions. 30
111. THEORETIACPAPRLO ACTHO MOLECULEWSIT H CARBONYBLO NDS. 30
A. Molecular-orbital and Valence-bond Descriptions of Carbonyl
.
Bonds 30
B. Excited States. 42
.
C. Electronic Structures of Conjugated Carbonyl Compounds 51
.
D. Radical Ions Derived from Aldehydes and Ketones 59
E. An Example of a Complete Quantum-mechanical Calculation :
.
the Ground State of Formaldehyde 66
JV. ACKNOWLEDGMENT.S 72
V. REFERENCES. 72
+
1 C.C.C. 1
2 G. Berthier and J. Serre
1. INTRODUCTION
In this chapter we shall deal with the physicochemical properties
and the theoretical treatment of carbonyl compounds. In the
carbonyl group, a very characteristic functional group of organic
chemistry, the bonds between the carbon and the oxygen atoms are
made up of and types, The oxygen atom bears two lone-pair
0 7r
electrons; one lone-pair orbital is mainly of type 2s, but the other
lonr:-pair orbital is of type 2p and its axis is directed perpendicularly
10 the direction of the rr orbitals. The main physicochemical properties
of carbonyl compounds are controlled by this electronic structure
and also by the geometrical position of the carbonyl bond. In an
aldehyde the functional group is necessarily located at a terminal
position in the molecule; in a ketone the group may be located in
another part of the molecule but the oxygen atom is still bound only
to one carbon. We will see in section I1 that the physicochemical
properties of carbonyl compounds are very homogeneous in the case
of aldehydes, and also in the case of those ketones where the carbonyl
group is not connected with another functional group. As the 2) lone
pair has its orbital directed in a direction perpendicular to that of
the rr bond, the lone-pair electrons cannot be conjugated with the
n- system, and the properties of this lone pair are relatively constant.
The properties connected with the rr electrons of the carbonyl bond
we also fairly constant, this bond being usually very slightly de-
localized. With pyridine or analogous compounds, there are two
unsaturated atoms in the vicinity of the nitrogen atom and the
heteroatom lone pair has a certain amount of s character which may
vary from one compound to another. Hence, the explanation of the
physicochemical properties is much less simple in these cases.
In section I11 the diffcrent possible theoretical treatments of
carbonyl compounds are given for the ground state and for some
excited states ; the theoretical treatment of some radicals derived
from carbonyl compounds is also outlined. In order not to repeat the
definitions of the essential concepts of quantum chemistry, section I11
is based on the chapter written by Coulson and Stewart in the first
volume of this series". The notation of these authors is kept as far as
possible, and many references are given in section I11 to equations
used by them (referred to, in parentheses, as C.S. followed by the
section number). However, the complete theoretical treatment of the
*
C. A. Coulson and E. T. Stewart in The Chenzistty of rll/;mes (Ed. S. Patai),
Interscience Publishers, London, 1964, pp. 1-147.