Quinonoid Compounds: Volume 1 (1974)

620 Pages·1974·16.608 MB·English

The chemistry ojthe quinonoid compounds
Edited by Saul Patai
Copyright ©@ 1974 John Wiley &L Sons Ltd. All Rights Reserved.
-
e chemistry of
Part 1
Edited by
SAULP ATAI
The Hebrew Utiiuersify,J ericsnlern
1974
JOHN WILEY & SONS
LONDON - NEW YORK - SYDNEY - TORONTO
An Interscience @ Publication
An Intersciensc 'a Publication
Copyright @ 1974 John Wiley &L Sons Ltd. All
Rights Reserved. No part of this publication
may be reproduced, stored in a retrieval system;
or transmittcd, in any form or by any nicans
electronic, mechanical, photocopying, recording
or otherwise, without ihe prior writtcn permission
of the Copyright owncr.
Library of Congress Catalog Card No. 73-17765
ISBN 0 471 66929 G
Printed iri Great Britaiti by
John Wright & Svm Lrd., (11 Tile Srotii>bridgeP ress, Bristol
H.-D. Becker Chahners University of Tcchnology and University of
Gothenburg, Gothenburg, Sweden.
R. Bentley F.A.S. University of Pittsburgh, Pittsburgh, U.S.A.
J. Gernstein University of the Negev, Beersheba, Israel.
St. Berger Cheniisches lnstitut der UniversitKt,Tubingen, Germany.
J. M. Bruce Manchester University, Manchester, England.
I. M. Campbell F.A.S. University of Pittsburgh, Pittsburgh, U.S.A.
J. Q. Chambers University of Tcnncssec, Knoxvillc, Tennessee, U.S.A.
M. D. Cohen Weizmann Institute of Science, Reliovot, Israel.
E. J. Fendler Tcxas A & M University, College Station, Texas, U.S.A.
J. H. Fen.d!Tr Tcxas A Sr M University, College Station, Texas, U.S.A.
K. T. Finley State University College, Brockport, New York, U.S.A.
M. I. Foreman University of Strathclydc, Glasgow, Scotland.
R. Foster University of Dundee, Dundce, Scotland.
G. J. Gleicher Oregon State University, Corvallis, Oregon, U.S.A.
R. Gompper Iiistitut fur Organische Chemie, Munich University,
Munich, Germany.
Hodge University of Lancaster, Lancastcr, England.
P.
L. Leiserowitz Weizmann Institute of Science, Rehovot, Israel.
A. S. Lindsey National Physical Laboratory, Teddi ngton, Middlesex,
England.
H. W. Moore University of California, lrvinc, California, U.S.A.
A. Rieker Cheniisches Insti tut dcr Universitiit, Tubingen, Germany.
R. H. Thomas University of Aberdeen, Aberdeen, Scotland.
T. A. Turney University of Aucklond, Auckland, New Zealand.
H.-U. Wagner lnstitut fur Organische Chemie, Munich University,
Munich, Gerniany.
R. J. Wikholm U i vers i t y of Ca I i for n i a, Irvi nc, Ca I i for i a, U .S .A .
n 11
K.-P. Zeller Chemiscties Institut der Uuiversitiit, Tubingen, Germany.
M. Zieliriski Institute of Chemistry of the Jagiellonian University of
Crxow, Poland.
V
Foreword
The present volume of the series ‘The Chemistry of Functional Groups’
is, like all other volumes of the series, organized according to the general
plan described in the Preface printed in the following pages.
This volume differs somewhat from the others previously published in
the series. The main dissimilarity lies in the fact that the quinonoid corn-
pounds do not have a functional group in the accepted sense, but rather
the whole molecule is the carrier of the quinonoid properties and rc?ac!Ions.
Moreover, the chemistry of quinones is inseparable in practice from the
chemistry of the corresponding hydroquinones. In addition, some types
of conipounds belonging to this class are riot quite accurately defined
(e.g. ‘non-benzenoid’ quinones).
The original plan also included the following chapters which did not
matcrialize: ‘ORD and CD of quinones and related compounds’ and
‘Quinhydrone and semiquinone systems’.
Jerusalem, July 1973 SAUL PATAI
vii
Preface to the series
The series ‘The Clieniistry of Functional Groups’ is planned to cover
in each volume all aspects of the chemistry of one of tlie important
functional groups in organic chemistry. The eniphssis is laid on the
functional group treated and on the effects whicli it exerts on tlie chemical
and physical properties, primarily in the immediate vicinity of the group
in question, and secondarily on thc bcliaviour of the whole molecule.
For instance, the volume The Clleiiiisfrjl of tile Efiier Liiiknge deals with
reactions in which tlie C-0-C group is involved, as wel! as with tlie
effects of tlic C-0-C group on tlie reactions of alkyl or aryl groups
coiiiiected to the ether oxygen. It is tlie purpose of the voluiiie to give a
complete coverage of al! properties and reactions of etlicrs in as far as
these depend on the presence of the ether group, but thc primary subject
matter is not the whole inolccule, but the C-0-C functional group.
A furtlicr restriction in tlie treatment of tlie various fuiictional groups
in these volumcs is that material 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
repented in detail, unless it is necessary for the balaiiccd treatment of the
subject. Therefore each of the authors is asked izot to give an eiicyclopaedic
coverage of his subject, but to coiicentrate 011 the most important recent
developnicnts and mainly on material that has not been adequately
covercd by reviews or other secondary sources by the time of writing of
tlic chapter, and to address Iiimself to a reader who is assumed to be at a
fairly zdvaiiced post-graduate level.
With these restrictions, it is realized that no plan can be devised for a
volume that would give a coiuplete coverage of tlic subject \villi 110 overlap
between chapters, wliile at the same time preserving the readability
of tlie text. The Editor set himself the goal of attaining rensonnhle coverage
with iiiodei.ate overlap, with a minimum of cross-references between tlie
chapters of each volume. this manner, su6cicnt freedom is given to
In
each author to produce rcndablc ~u~~si-ll~oilo~c~hanppltcirisc.
ix
Preface to the series
X
The gerieral 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 molecde, 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, nuclezr 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 coiijunctioii
with other reagents.
(e) Special topics which dc not fit any of the above sections, such as
photochemistry, radiation clieniis t ry, biochemical format ions 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 plaiined (e.g a chapter 011 ‘Thioketones’
is included in the volume The Ciiemistry of the Curbony1 Grotcp, and a
chapter on ‘Ketencs’ is included in the volume The Clteri?istry of Alkenes).
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. ‘Polycthers’ in The Cimnistrj1 of the Elher Litiknge,
or ‘Tetraaminoethyleries’ in The CJiet?iistry of the Ariiirio Grozcp.
This plan entails that the breadth, depth and thought-provoking nature
of each chapter will differ with the views and iuclinatiorx of the autiior
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
consideration to the originally planned logical order of the chapters.
If after the appearance of the oriSiiially planned parts of a volume it is
found that either owing to non-delivery of chapters, or to new develop-
ments in the subject, suflicieiit material has accumulated for publication
of an additional part, this will be done as soon as possible.
Preface to the series xi
The overall plan of the volumes in the series ‘The Chemistry of
Functionai Groups’ includes the titles listed below:
The Chemistry of Alkenes (published in two volumes)
The Chemistry of the Carboiijd Group (published in two uolimiess)
The Chemistry of the Ether Linkage (published)
The Chemistry of the Amino Gsoup (published)
The Chenzistry of the Nitro and the Nitroso Group (picblished in two parts)
Tke C/iernistr.y of Carboxylic Acids and Esters (published)
The Cheniistry of the Carbon-Nitrogen Double Bond (published)
The Clienzistry of the Cyan0 Group (published)
The Chemistry of Ainides (published)
The Chemistry of the Hydroxyl Group (published in two parts)
The Chemistry of the Azido Group (published)
The Chemistry of Acyl Halides (published)
The Cliemistry of the Carbon-Halogen Bond (publislied iii tirto pnrts)
The Cheniistry of the Quinonoid Coinpounds (published ill tvfop nrts)
The Chmiistry of the Thiol Group (in prepasation)
The ChenzistrJJo f the Carboii-Carbon Triple Bond
The Chemistry of Aniidiiies and Iniidales (in preparation)
The Chemistry of the Hydrazo, Azo mid Azoxy Groups (in preparation)
Tie Chemistry of the SO, -SO,, -SO&? and -SO& Groups
The Cheinistry of the --OCN, --NCO, -SCN mid --NCS Groups
The Clientistry of the -PO,H, and Related Groups
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 forentost
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 nanie). 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 2. 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, SAULP ATAI
.
.I eru s;i lem I SILAI :L
contents
1. Theoretical and general aspects I
G. J. Gleichcr
2. The structural chemistry of quinones 37
J. Bernstcin, M. D. Colien and L. Leiserowitz
3. Synthesis 111
R. H. Thomas
4. Identification and determination of quinones 163
St. Berger and A. Rieker
5. Mass spectra of quinones 231
K.-P. Zeller
6. Quinone complexes 257
R. Foster and M. I. Foreman
7. Quinones as oxidants and dehydrogenating agents 335
H.-D. Becker
8. Rearrangements of quinones 425
H. W. Moore and R. 3. Wikholin
9. Photochemistry of quinones 465
J. M. Bruce
10. Radiation chemistry of quinones 539
J. H. Fendler and E. J. FendIer
11. Fragmentation reactions of quinones 579
P. Hodge
12. Syntheses and uses of isotopically labelled quinones 61 7
M. Zdiiiski
13. Biological reactions of quinones 683
R. Beiitlcy and 1. M. Campbell
14. Electrochemistry of quinones 737
J. Q. Chambers
15, Polymeric quinones 793
A. S. Lindsey
16. Non-benzenoid quinones 857
T. A. Turiiey
...
XI11
xiv Contents
17. The addition and substitution chemistry of quinones 877
K. T. Finley
18. Quinone methides 1145
H.-U. Wagner and R. Gornpper
Author index 1179
Subject index 1247
The Chemistry of the quinonoid compounds
Edited by Saul Patai
Copyright @© 1974 John Wiley &L Sons Ltd. All Rights Reserved.
1
CHAPTER
Theoretical an
GERALDJA Y GLEICI-JER
Departinen f of Chemistry, Or'egott Srate Utriversi~yC, omaf lis,
Oregon, U.S.A.9 7331
1. INTRODUCT.I ON 1
ir. THEORETICTARLE ATMEONFT Q UII YON ES . 2
.
111. PHYSICAL PROPERTIES OF QUINONES G
A. Thermochemistry . G
B. Structure . S
C. Dipole Moments. . 13
D. Magnetic Susceptibilities . . 14
E. Reduction Potentials . . 17
F. lnfrared Spectroscopy . . 21
G. Ultraviolet Spectroscopy . . 24
H. Nuclear Magnetic Resonance Spectroscopy . 26
IV. QUINODODIMETHANES . 26
V. ACKNOWLEDGMENT. S . 30
VI. REFERENCES . . 30
1. lNTR0DUCTION
Molecules possessing the quinonoid structure should, at first inspection,
present no special problem to a student of structural chemistry. The
alternating system of single and double bonds, including as it does exo-
cyclic moieties, could be considered as a simple crossconjugated system.
This is true both if the exocyclic group is heteroatomic, as in the cases of
quinones and quinonediirnines 1, or if the molecule is polyolefinic in
4
nature such as quinododimethanes 2.
X
(la) X = 0
(fb) X = NH
1