Amino, Nitrosco and Nitro Compounds and Their Derivatives: Volume 1 (1982)

718 Pages·1982·18.97 MB·English

Supplement F The Chemistry of Amino, Nitroso and Nitro Compounds and their Derivatives
Edited by Saul Patai
Copyright 0 1982 by John Wiley & Sons Ltd. All rights reserved.
Supplement F
The chemistry of
Part 1
Edited by
SAULP ATAI
The Hebrew University, Jerusalem
JOHN WILEY & SONS
CHICHESTER- NEW YORK- BRISBANE - TORONTO - SINGAPORE
An Interscience 8 Publication
1982
Copyright 0 1982 by John Wiley & Sons Ltd.
All rights reserved.
No part of this book may be reproduced by any means,
nor transmitted, nor translated into a machine language
without the written permission of the publisher.
Library of Cataloging in Publication
Congress Data
Main entry under title:
Supplement F.
(The Chemistry of functional groups)
“An Interscience publication.”
Includes index
1. Amino compounds. 2. Nitroso-compounds.
3. Nitro compounds. I. Patai, Saul. 11. Title:
The Chemistry of amino, nitroso, and nitro compounds
and their derivatives. 111. Series.
QD305.A8S95 547l.04 81-16153
ISBN 0-471-27873-4 (set of 2 VOlS). AACR2
British Library CataIoguing in Publication Data:
The Chemistry of amino, nitroso and nitro
compounds and their derivatives-(The Chemistry
of functional groups. Supplement F)
Part 1
1. Nitrogen compounds
I. Patai, Saul 11. Series
547’. 041 QD181.Nl
ISBN 0 471 27871 8
ISBN 0 471 27873 4 (set of 2 vols)
Typeset Preface Ltd., Salisbury, Wiltshire,
by
and printed in the United States of America
by Vail-Ballou Press, Inc., Binghamton, N.Y.
Contributing Authors
R. W. Alder School of Chemistry, University of Bristol, Bristol BS8 ITS,
England
H. G. Aurich Fachbereich Chernie, Philipps-Universitat Marburg, Marburg,
Germany
L. Ratt Department of Chemistry, University of Aberdeen, Aberdeen
AB9 2UE, Scotland
I?. J. Baurngarten Department of Chemistry, University of Illinois at Chicago
Circle, Box 4348, Chicago, Illinois 60680, U.S.A.
D. K. Bohrne York University. Downsview, Ontario, Canada
E. Brauer Department of Pharmaceutical Chemistry, The School of
Pharmacy, The Hebrew University, Jerusalem, Israel
W. Britton Chemistry Department, The University of Texas at Dallas,
E.
Richardson, Texas 75080, U.S.A.
E. Buncel Department of Chemistry, Queen’s University, Kingston
K7L 3N6, Ontario, Canada
E. P. Burrows U.S. Army Medical Bioengineering Research and Development
Laboratory, Fort Detrick, Frederick, Maryland, U.S.A.
B. C. Challis Chemistry Department, Imperial College, London, United
Kingdom and New England Institute for Life Sciences, Waltham,
Massachusetts, U.S.A.
J. A. Challis Chemistry Department, Imperial College, London, United
Kingdom and New England Institute for Life Sciences, Waltham,
Massachusetts, U.S.A.
Y. L. Chow Department of chemistry, Simon Fraser University, Burnaby,
B.C., Canada
V. A. Curtis Department of Chemistry, University of Illinois at Chicago
Circle, Box 4348, Chicago, Illinois 60680, U.S.A.
L. Duhamel UniversitC de Rouen, Facultt des Sciences et des Techniques,
761 30 Mont-Saint-Aignan, France
H. Feuer Department of Chemistry, Purdue University, West Lafayette,
Indiana 47907? U.S.A.
A. J. Fry Wesleyan University, Middletown, Connecticut, U.S.A.
J. Greenblatt Department of Chemistry, Wayne State University. Detroit,
Michigan 43202, U.S.A.
V
vi Contributing Authors
C. L. Greenstock Medical Biophysics Branch, Atomic Energy of Canada Limited,
Whiteshell Nuclear Research Establishment, Pinawa, Manitoba,
Canada
E. Grushka Department of Inorganic and Analytical Chemistry, The Hebrew
University, Jerusalem, Israel
A. M. Halpern Department of Chemistry, Northeastern University, Boston,
Massachusetts 021 15, U.S.A.
N. Kornblum Department of Chemistry, Purdue University. West Lafayette,
Indiana, U.S.A.
K. Levsen Institut fur Physikalische Chemie, Universitat Bonn, Bonn,
West Germany
E. S. Lewis Department of Chemistry, Rice University, Houston, Texas
77001, U.S.A.
G. Pitacco Institute of Chemistry. University of Trieste, Italy
Raban Department of Chemistry, Wayne State University, Detroit,
M.
Michigan 48202, U.S.A.
G. N. Robinson Department of Chemistry, University of Aberdeen, Aberdeen
AB9 2UE, Scotland
D. H. Rosenblatt U.S. Army Medical Bioengineering Research and Development
Laboratory, Fort Detrick. Frederick, Maryland, U.S.A.
H. Schwarz Institut fur Organische Chemie, Technische Universitat Berlin,
Berlin, West Germany
R. B. Sessions Institut Le Bel, Universitt Louis Pasteur. 1 Rue Blaise Pascal,
67008 Strasbourg. France
T. Sheradsky Department of Organic Chemistry, The Hebrew University,
Jerusalem. Israel
H. E. Smith Department of Chemistry, Vanderbilt University, Nashville,
Tennessee 37235, U.S.A.
P. J. Smith Department of Chemistry and Chemical Engineering, University
of Saskatchewan, Saskatoon. Saskatchewan, Canada
S. Sorriso Dipartimento di Chimica, Universita di Perugia, 0610 0 Perugia,
Italy
Y. Tapuhi Department of Inorganic and Analytical Chemistry, The Hebrew
University, Jerusalem, Israel
E. Valentin Institute of Chemistry, University of Trieste, Italy
K. C. Westaway Department of Chemistry, Laurentian University, Sudbury,
Ontario, Canada
D. L. H. Williams Chemistry Department, University of Durham, Durham,
England
Foreword
The present Supplement F includes material on nitrogen-containing functional groups
such as amino, nitroso and nitro groups. In the main volumes of the Chemistry of the
Functional Groups Series, these groups have been treated in the following books:
The Chemistry ofthe Amino Group (19 68);
The Chemistry of the Nitro and Nirroso Groups, Part 1 (1969) and Part 2 (1970).
In addition, several functional groups which have not been treated in the main
volumes have also been included, such as nitrones, nitronic acids, nitroxides, nitro-
samines, nitrosoimines, enamines and ynamines.
With the exception of a chapter on ‘Ipso-attacks involving NOz groups’, all chapters
planned for this Supplementary Volume actually materialized.
The editor will be very grateful to readers who would communicate to him omissions
or mistakes relating to this volume as well as to other volumes in the series.
Jerusalem, July 1981 SAUL PATAI
vii
The Chemist9 of Functiomal 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 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 Chetnistry of the Ether Litikage 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 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 materiai included in easily and generally available secondary or tertiary
sources, such as 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 tiot to give an encyclopaedic 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 Icvel.
With these restrictions, it is realized that no plan can be devised for a volume that
would give a cotnpletc coverage of the subject with no overlap between chapters,
while at the same time preserving the readability of ;he text. The Editor set himself the
goal of attaining recrsotwble coverage with moderate 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.
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 deter-
ix
X Preface to the series
mination including chemical and physical methods, ultraviolet, infrared, nuclear
magnetic resonance and mass spectra: a chapter dealing with activating and direc-
tive 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 photo-
chemistry, radiation chemistry, biochemical formations and reactions. 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 Chetnistry of the
Carbonyl Group, and a chapter on ‘Ketenes’ is included in the volume The Chemistry
of Alkenes). In other cases certain compounds, though containing only the func-
tional group of the title, may have special features so as to be best treated in a separate
chapter, as e.g. ‘Polyethers’ in The Chetnistry of the Ether Linkage, or ‘Tetraamino-
ethylenes’ in The Chemistry of the Amino 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 somqwhat uneven. Moreover, s 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-delivery of chapters, or to new developments in the subject,
sufficient material has accumulated for publication of a supplementary volume,
containing material on related functional groups. this will be done as soon as possible.
The overall plan of the volumes in the series ‘The Chemistry of Functional Groups’
includes the titles listed below:
The Chemistry of Alketies (two volumes)
The Chemistry of ihe Carbonyl Group (two volumes)
The Chemistry of the Ether Linkage
The Chemistry of the Amino Group
The Chemistry of the Nitro and Nitroso Groups (two parts)
The Chemistry of Carboxylic Acids and Esters
The Chemistry of the Carbon-Nitrogen Double Bond
The Chemistry of the Cyano Group
The Chemistry of Amides
The Chemistry of the Hydroxyl Group (two parts)
The Chemistry of the Azido Group
The Chemistry of Acyl Halides
The Chetnistry of the Carbon-Halogen Bond (two parts)
The Chemistry of Quinonoid Compounds (two parts)
The Chemistry of the Thiol Group (two parts)
The Chetnistry of Atnidities arid Imidates
The Chemistry of the Hydrnzo, Azo atid Azoxy Groups (two parts)
The Chemistry of Cyaiiates and their Thio Derivatives (two parts)
The Chemistry of Diazotiiutn arid Diazo Groups (two parts)
The Chemistry of the Carbon-Carbon Triple Bond (two parts)
Supplemetit A: The Chetnistr-y of Double-bonded Functional Groups (two paris)
Preface to the series xi
Supplement B: The Chemistry of Acid Derivatives (two parts)
The Chemistry of Ketenes, Alleties and Related Coinpounds (two parts)
Supplenient E: The Chemistry of Ethers, Crown Ethers, Hydroxyl Groups and their
Sulphur Analogues (two parts)
The Chemistry of the Sulphoniurn Group (two parts)
Supplement F: The Chemistry of Amino, Nitroso and Nitro Groups and their
Derivatives (two parts)
Titles in press:
The Chemistry of Peroxides
The Chemistry of Organornetallic Coinpounds
Supplement C: The Chemistry of Triple-bonded Functional Groups
Supplement D: The Chemistry of Halides and Pseudo-halides
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 continued, 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 invaluable aid (but unfortunately their
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 due to all of them, especially to Professor Z. Rappoport.
Carrying out such a long-range project would be quite impossible without the non-
professional but none the less essential participation and partnership of my wife.
The Hebrew University
Jerusalem, I s R A E L SAUL PATAI
Contents
1. Structural chemistry 1
S. Sorriso
2. Stereochemistry and conformations 53
M. Raban and J. Greenblatt
3. The chemistry of ionized amino, nitroso and nitro compounds in the gas
phase 85
H. Schwarz and K. Levsen
4. Rearrangements involving nitroso and nitro compounds 127
D. L. H. Williams
5. The spectroscopy, photophysics and photochemistry of saturated amines 155
A. M. Halpern
6. Photochemistry of nitro and nitroso compounds 181
Y. L. Chow
7. Radiation chemistry of amines, nitro and nitroso compounds 291
C. L. Greenstock
8. Electrochemistry of nitro compounds 31 9
A. J. Fry
9. Electrochemistry of amines 339
W. E. Britton
10. Radical anion reactions of nitro compounds 36 1
N. Kornblum
11. Direct aminations 395
T. Sheradsky
12. Pyrolysis of nitrites, nitrates, nitro compounds, nitroso compounds and
amines 41 7
L. Batt
13. Nitrones and nitronic acid derivatives: their structure and their roles in
synthesis 459
E. Breuer
14. Nitroxides 565
H. G. Aurich
15. Enamines and ynamines 623
G. Pitacco and E. Valentin
...
XI11
xiv Contents
16. Nitro-activated carbon acids 71 5
E. S. Lewis
17. Gas-phase basicity and acidity of amines 731
D. K. Bohme
18. Special properties of di- and poly-amines 763
R. W. Alder and R. B. Sessions
19. Alkyl nitrate nitrations 805
H. Feuer
20. Aminals 849
L. Dahamel
21. Detection and determination of nitro and nitroso compounds 909
Y.T apuhi and E. Grushka
22. Deaminations (carbon-nitrogen bond cleavages) 929
R. J. Baumgarten and A. Curtis
V.
23. Chiroptical properties of amino, nitroso and nitro compounds 999
H. E. Smith
24. Thermochemistry of nitro compounds, amines and nitroso compounds 1035
L. Batt and G. N. Robinson
25. Oxidation of amines 1085
D. H. Rosenblatt and E. P. Burrows
26. N-Nitrosamines and N-nitrosoimines 1151
B. C. Challis and J. A. Challis
27. The role of Meisenheimer or a-complexes in nitroarene-base interactions 1225
E. Buncel
28. Uses of isotopically labelled amino, quaternary ammonium and nitro
compounds 1261
P. J. Smith and K. C. Westaway
Author Index 1313
Subject Index 1399