Diazonium and Diazo Groups: Volume 2 (1978)

564 Pages·1978·14.928 MB·English

The Chemistry of Diazonium and Diazo Groups
Edited by Saul Patai
Copyright 0 1978 by John Wiley & Sons Ltd. All rights reserved.
The chemistry of
diazonium and diazo groups
Part 2
Edited by
SAULP ATAI
The Hebrew Utiiuersity, Jerusaletii
1978
JOHN WILEY & SONS
CHICHESTER - NEW YORK - BRISBANE - TORONTO
An In ferscierice 61P ttblicafioii
Copyright @ 1978 by John Wiley & Sons Ltd.
Reprinted February 1979.
All rights reserved.
No part of this book may bc reproduced by any means,
nor transmitted, nor translated into ;1. machine language
without the written permission of the publisher.
Library of Congress Catalog Card No. 75-6913
ISBN 0 471 99492 8 (Pt. I)
ISBN 0 471 99493 6 (Pt. 2)
ISBN 0 471 99415 4 (Set)
Printed in Great Britain by Page Bros (Norwich) Ltd.
Mile Cross Lane. Norwich.
Contributing authors
W. Ando Chemistry Department, The University of Tsukuba, Niiharigun,
Ibaraki 300-3 1, Japan
D. A. Ben-Efraim The Weizmann Institute of Science, Rehovot, Israel
C. F. Cooper Department of Chemistry, University of Missouri-Rolla, Rolla,
Mo. 65401, USA
A. J. Fry Wesleyan University, Middletoum, Connecticut, USA
A. F. Hegarty Chemistry Department, University College, Cork, Ireland
E. S. Lewis Department of Chemistry, Rice University, Houston, Tesas, USA
G. Linstrumelle Equipe de Recherche No. 12 du CNRS, Laboratoire de Chimie,
Ecole Normale Superieure, Paris, France
J. F. McGarrity Institute of Organic Chemistry, University of Lausanne,
Lausanne, S\vitzerland
J. Moffat Department of Chemistry, University of Waterloo, Waterloo,
6.
Ontario, Canada
H. M. Nienieyer Institute of Organic Chemistry, University of Lausanne,
Lausanne, Switzerland
M. Regitz Department of Chemistry, University of Kaiserslautern, D-6750,
Federal Republic of Germany
K. Schank Fachbereich 14.1 Organische Cheniie, Universitiit des Saarlandes,
D-6600 Saarbrucken, Germany
R. Shaw 1 162 Quince Avenue, Sunnyvale, California 94087, USA
P. J. Smith Department of Chemistry and Chemical Engineering, University
of Saskatchavan, Saskatoon, Saskatchc\van, Canada
S. Sorriso Istituto di Chirnica Fisica, Uni\*ersitB di Perugia, 06100 Periigia,
Italy
V. Sterba Organic Chemistry Department, Institute of Chemical Techno-
logy, 532 10 Pardubice, Czechoslovakia
K. C. Westaway Department of Chemistry, Laurentian University, Sudbury,
Ontario, Canada
D. Whittaker Department of Organic Chemistry, University of Liverpool,
England
S. Wulfman Department of Chemistry, University of Missouri-Rolla, Rolla,
D.
Mo. 65301, USA
V
Foreword
The present volume, ‘The Chemistry of Diazonium and Diazo Groups’ is, on the
whole, organized and presented according to the general lines described in the
‘Preface to the Series’, printed on the following pages.
Some difficulty arose in the presentation o’wing to the fact that while the two groups
treated, i.e. the diazo group and the diazoniuni group, are closely related and even
occur irk equilibrium with each other, their chemical behaviour and characteristics
differ from each other considerably. Moreover, the material which had to be covcred
proved to be much more extensive than originally surmised. For these reasons,
some of the subjects had to be divided into two or more chapters; for instance, the
synthetic applications of diazoniuni and diazo groups are treated in two separate
chapters and even so each of thcse turned out to be very large. Similarly, the
syntheses of the different title compounds are discussed in three separate chapters.
The plan of the present volume also included a chapter on ‘Biological and
Pharmaceutical Effects’ which, however, failed to materialize. It is hoped that this
will appear in one of the supplementary volumes to the series.
Jerusalem, February 1977 SAUL PATAI
Vii
The Chemistry of Functional 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 Chemistry of [lie Elirer Liriknge deals with
reactions in which the C-0-C group is involved, as well as \vith the effects of the
C-0-C group on the reactions of nlkyl 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
voluines 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 librarics 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 riot to give an encyclopaedic
coverage of his subject, but to concentrate on the most iniportant recent develop-
ments 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 level.
With these restrictions, it is realized that no plan can be dcvised for a volume that
would give a cortiplcle coverage of the subject with ti0 overlap betiyeen chapters,
while at thc same time preserving the readability of the text. The Editor set himself
the goal of attaining r~cnsotin6lcc overage with modcr.n/c 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 qu3si-moiiogrnphic chapters.
The general plan of each volume includes the following main scctions:
(a) An introductory chapter dealing with the general and theorctical aspects of
the group.
(b) One or more chapters dealing \vith the formation of the functional group in
question, either from groups present in the molecule, or by introducins the new group
directly or indircctlj.
(c) Chapters describing the characterization and characteristics of the functional
groups, i.e. a chaptcr dcaling with qualitative and quantitative nlethods of detcr-
mination including chemical and physical methods, ultraviolet, infrdred, nuclear
IS
X Preface to the series
magnetic resonance and mass spectra: a chapter dcaling with activating and
directive effects exerted by the group and/or a chaptcr on the basicity, acidity or
complex-forming ability of the group (if applicable).
(d) Chapters on the reactions, traIisforniations 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 ‘Thioketoncs’ is includcd in the voliime Tlie Cliemistry
of the Curbotiyl Gt-oi/p,a nd a chapter on ‘Ketenes’ is included in the volume The
Clieniistry of Alketies). In otha cases certain compounds, though containing only
the functional group of the title, niay have special features so as to bc best treated in
a separate chaptcr, as e.g. ‘Polyethers’ in The Chettiisrt.y of the Etlicr Litikage, or
‘Tetraaminoethylencs’ in Tlie Chetliistry of rhe Aniirio Groicp.
This plan entails that the breadth, dcpth and thought-provoking nature of each
chapter will differ with the views and inclinations of the au!hor and the presentation
will rtecessarily be somewhat uneven. Morcovcr, a serious problem is caused by
authors who deliver their manuscript late or not at all. In ordcr to overcome this
problein at least to sonic cstent, it was dccided to publish certain volumes in several
parts, without giving consideration to the originally planned logical order of tlie
chapters. If after the appearance of the originally planned parts of n volume it is
found that either owing to non-delivery of chapters, or to ncw developments in the
subject, sufficient inaterial has accumulated for publication of a supplementary
volume, containing inaterial 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 Clietriistry of Alkcries (two voliimes)
The Clrcniistry of the Curbotiyl Groicp (two voluttics)
The Cliettiistt-y of the Ether Linkage
The Clictiiistry of the .4tnino Groicp
The Clicttiistry of ~licN itro atid Nitroso Groicp (two parts)
The Cliettiistry of Cat.hoxylic Acids atid Esters
The Clrcinistry of the Cnr.bori- Nitrogetr Doirble Bond
Tlie Cliemistry of tlie Cyutio Groiip
Tlie Clicttiistry of Attiirks
The Cliettiistry of the Hyrlr.o.uy1 Groiip (twop arts)
Tlie Clieniistry of the Azido Groirp
The Cliettiistry of AcyI Halides
Tlre Cheniistry of the Carbon- Hoiog~trB od (tLc.0 parts)
Tlie Chemistry of Qieitiotioid Cottipoiitids (two parts)
Tlte Cliemistry of the Tliiol Groicp (two parts)
Tlie Cheniistry of Attiiditics arid Ittiiclcitcs
The Cliettiistry of rlie Hyclrczzo, Azo arid Ai0.V)’ Grorips
The C1rettiisfr.yo f Cyatiotcs ntitl tlicir Tliio Dcricarii.c.s
The Clicttiistry of Diazotiiiitti nticl Dia;o Groicps
Siipplettietit A: Tlie Cliettiisrry of Double-Boritled Firrictioirnl Groirps (two pclrts)
Preface to the series xi
Titles in press:
The Chemistry of rlie Carbon-Carbori Tsiple Bod b
Siippletnerit B: The Cliettiistry of Acid Deriratices
Future volumes planned include:
Tlic Clicmislry of Ciiniiilcnes arid Hctcr~ocirttiirlctics
The Clieniisfryo f Organonictnllic Conipoiuirls
The Clionistry of Sirlpliirr-cotitninirig Cot~ipoii~ids
Sirpplenierit C: Tlie Clieniistry of Triple-bonded Fiirictiotial Croirps
Sirpplcnient D: Tlrr Clieniisrry of Halides arid Pseirdo-liulidcs
Sfipplenietit E: The Clietnistry of --NH2, -OH, a d -SH Groirps otid their
Dericntives
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 thesc is Dr Arnold
Weissberger, whose reassurancc and trust encouraged me to tackle this task, and who
continues to help and advise me. The eficient and patient cooperation of several
staff-members of thc 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 SAUL PATAI
Jerusalem, ISRAEL.
Contents
General and theoretical aspects of the diazonium and diazo groups 1
1.
J. B. Moffat
Diazonium-diazo equilibrium 71
2.
V. StErba
Structural chemistry
3. 95
S. Sorriso
Thermochemistry of diazo compounds and organic azides
4. 137
R. Shaw
Detection and determination of diazo and diazonium groups
5. 149
D. A. Ben-Efrairn
6. Basicity, acidity and hydrogen bonding
179
J. F. McGarri:y
Complex formation
7. 231
H. M. Nierneyer
Synthetic applications of diazonium ions
8. 247
D. S. Wulfman
Photochemistry of the diazonium and diazo groups
9. 341
W. Ando
10. The electrochemistry of the diazo and diazonium groups
489
A. J. Fry
The influence of the diazo and diazonium groups
11. 499
E. S. Lewis
12. Kinetics and mechanisms of reactions involving diazonium and diazo
groups I
51
A. F. Hegarty
Rearrangements involving the diazo and diazonium groups
13. 593
B. Whittaker
14. Preparation of diazonium groups 645
K. Schank
15. Synthesis of diazoalkanes 659
M.R egitz
16. Preparation and uses of isotopically labelled diazonium and diazo
compounds
709
P. J. Smith and K. C. Weslaway
...
Xlll
xiv Contents
17. Carbonyl, phosphoryl and sulphonyl diazo compounds 75 1
M. Regitz
18. Synthetic application of diazoalkanes, diazocyclopentadienes and
diazoazacyclopentadienes 821
D. S. Wulfman, G. Linstrumelle and C. F. Cooper
Author Index
977
Subject Index 1045
The Chemistry of Diazonium and Diazo Groups
Edited by Saul Patai
Copyright 0 1978 by John Wiley & Sons Ltd. All rights reserved.
12
CHAPTER
Kinetics and mechanisms of
reactions involving diaztanium
and diazo groups
A. F. HEGARTY
Chemistry L)epartr?ietit, Utiiuersity College, Cork, Irclnrid
I. INTRODUCTION. . . 512
11. DIAZOTIZATION . 514
A. Low Acidities xi) . . 515
([H+]<
B. Intermediate Acidities (10-2-10-' hi [ti+]) . . 516
C. Moderate Acidities (0.1-6.5 xi [H+]) . . 516
D. Concentrated Acid . 518
E. Halide Ion Catalysis . . 519
F. Non-aqueous Solvents . . . 519
111. REACTIOKOSF ARENEDlAZONIUhl IONS . . . 520
A. Replacement of Nitrogen by Nucleophiles (Dediazonration) . . 520
1. Phenyl cation pathway . . 521
2. Isotope effects . . 522
3. Selectivity and structure of phenyl cation . . 522
4. Substituent effects . . . 523
5. Schieniann reaction. . 525
6. Bimolecular mechanisms . . . 525
7. Nitrogen rearrangement accompanying hydrolysis . . 526
8. Benzyne formation . . . 528
B. Reaction of Nucleophiles at the Tcrminnl Nitrogen. . 530
i. Oxygen nucleophilcs . . 532
a. Hydroxide ion . . 532
i. Isomcrization of diazolates . . 532
ii. Reaction of diazotates with acid . . 534
iii. Alkanediazotates . . 537
iv. Acid catalysis . . 538
v. Structure of 'diazoliyiroxide' . . . 539
b. Alkoxide . . 539
c. Phenoxide . . . 540
d. Acetate . . 541
e. Diazotate . . . 541
2. Sulphur nucleophilcs . 541
3. Carbon nucleophiles . , 542
a. Cyanide ion . . 542
b. Ketones and related compounds . . 543
c. Other carbanions . . 545
d. Aromatic substrates . . 545
i. Site of coupling . . 546
ii. Reactivity of arenediazoriium ions . . 547
51 1