Chemistry of Heterocyclic Compounds. Volume 1. The Heterocyclic Derivatives of Phosphorus, Arsenic, Antimony and Bismuth

799 Pages·2016·33.58 MB·English

by  Mann F.G.

THE HETEROCYCLIC DERIVATIVES OF
PHOSPHORUS, ARSENIC, ANTIMONY
AND BISMUTH
This ia the second &&on oj lhejrst volume in the series
CHEMISTRY HETEROCYCLIC COMPOUNDS
THE OF
THE CHEMISTRY HETEROCYCLIC COMPOUNDS
OF
A SERIES OF MONOGRAPHS
A. WEISSBERGER and E. C. Editors
TAYLOR,
The Heterocyclic Derivatives of
PHOSPHORUS, ARSENIC, ANTIMONY
and BISMUTH
SECOND EDITION
1970
WILEY-INTERSCIENCE
a division John Wiley & Sons
of
- - -
New York London Sydney Toronto
Copyright 0 I970 by John Wiley and Sons, Inc.
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 photo-copying, recording or
otherwise, without the prior written permission of
t.he copyright owner.
of Congreaa Catalog Card Nutnber: 75-1 10402
Library
ISBN-1 3: 978-0-47 1-37489-3
ISBN 471
0 37489 X
The Chemistry of Heterocyclic Compounds
The chemistry of heterocyclic compounds is one of the most complex
branches of organic chemistry. It is equally interesting for its theoretical
implications, for the diversity of its synthetic procedures, and for the
physiological and industrial significance of heterocyclic compounds.
A field of such importance and intrinsic difficulty should be made as
readily accessible as possible, and the lack of a modern, detailed and
comprehensive presentation of heterocyclic chemistry was therefore
keenly felt. It is the intention of the present series to fill this gap by
expert presentation of the various branches of heterocyclic chemistry.
The subdivisions have been designed to cover the field in its entirety by
monographs which reflect the importance and the interrelations of the
various ring systems, and accommodate the specific interests of the
authors.
In order to keep The Chemistry of Heterocyclic Compounds up to date,
two methods will be applied in accordance with the nature of the
respective compound group and the timeliness of the respective Volume
of the First Edition. For those areas where the Volumes have become
obsolete by overwhelming progress, new editions are planned. For those
areas where the necessary changes are not too great, supplements to the
respective volumes will be published. In this way, we will achieve our
purpose with a minimum of new investments for the subscriber to the
whole set.
The series started in 1950 with a slim volume by Frederick George
Mann on the Heterocyclic Derivatives of Phosphorus, Arsenic, Anti-
mony, Bismuth, and Silicon. Great progress in these fields has been
made and we are, therefore, pleased to publish a new edition of Dr.
Mann's book.
December 1968 A. WEISSBERGER
E. C. TAYLOR
V
Yet all experience is an arch wherethro'
Cleaw that untravell'd world, whose margin fades
For ever and for ever when I moue.
TENNYSON
In the First Edition of this work, published in 1950, an attempt was
made to give ‘a systematic account of the heterocyclic organic deriva-
tives of phosphorus, arsenic, antimony, bismuth (and silicon), that is to
say, of those derivatives which contain these elements and carbon (with
or without other elements) in the ring system’, and this object was
achieved in 162 pages of text. The subsequent vast expansion of our
knowledge of heterocyclic organic chemistry has presented the author
with a massive task: for example, by 1963 there were about 150 different
ring systems containing phosphorus and about 160 such systems
containing arsenic, and these numbers are rapidly increasing.
In these circumstances some selection has been inevitable: in this
Second Edition I have had to omit a number of systems of which very
little is known and which appear to be (at present) of small interest. My
original intention, moreover, was to deal only briefly with rings in which
the Group VB element, X, was present as -0-X(R)--C- or, more
particularly, as -0-X(R)-0-, with the atom X often oxidized,
because such systems are really cyclic esters, frequently vulnerable to
hydrolysis, and thus markedly different from the highly stable ring
systems containing solely carbon and the heteroatoms. This intention
has often failed, however, because our knowledge of several such systems
is based on a considerable volume of work, much of which is of great
interest and importance.
It should be emphasized that this volume is one of a series on
organic heterocyclic compounds, and consequently purely inorganic
rings, i.e., those devoid of carbon as a ring member, are omitted; this
would in any case have been essential, for certain inorganic ring systems
such as the phosphonitriles have already received separate volumes in
their own right.
In the First Edition of this book, the heterocyclic derivatives of
silicon occupied two pages : our current knowledge of this subject would
also require a separate volume, and the cyclic derivatives of silicon have,
therefore, also had to be omitted from this Edition.
The order in which the heterocyclic systems are presented is shown
in the Table of Contents (p. : taking phosphorus as an example, rings
xv)
containing carbon and one phosphorus atom are discussed in order of
ix
x Preface
increasing size of ring; rings containing carbon and two or more phos-
phorus atoms follow in the same order; finally rings containing phos-
phorus and another heteroatom, usually in order of increasing atomic
weight of this are considered, each group also in order of increasing
atom,
size of ring.
An important factor in book of this type is the nomenclature. It is,
a
I think, abundantly clear that the only acceptable system is that of the
Ring Index (2nd Edition) and its Supplements (p. xiii). The authors of
the Ring Index, working in consultation with the Nomenclature
Committees of the International Union of Pure and Applied Chemistry
(IUPAC), have produced a logical and flexible system for the naming,
numbering, and presentation of more than 14,000 homocyclic and
heterocyclic rings (p. xiii).
In the present Edition, each ring system is discussed in its own
section, which is headed by the Ring Index name and gives the number,
mode of presentation of the ring, and its notation : the ring (with certain
exceptions) is shown in its lowest state of hydrogenation, and any
modification of the name for hydrogenated derivatives is stated.
The adoption of Ring Index names is rapidly becoming general.
The older names were, however, widely used until recently and some
still persist: these names are usually given in each section, so that a
chemist having occasion to consult one of the older chemical indexes
can find the entry he seeks.
The Ring Index in certain cases retains a familiar and/or long
established trivial name for a ring system : all other names are based on
the rules fully explained in the Second Edition of that work. The Ring
Index has one minor disadvantage, namely, that a hydrogenated and
heavily substituted ring system may develop a rather long name. This
is offset by the fact that every ring system now has its own name and
number. In particular, when derivatives of a ring system have been
prepared or investigated by organic chemists, biochemists, pharma-
cologists, physiologists, and workers in other fields, a remarkable variety
of names may have been employed (cf. for example 1,3,2-&oxaphosphor-
inanes, Part I, pp. 295-301) : this confusion of names should be rapidly
reduced by adoption of the Ring Index system.
In the Foreword to the First Edition, I briefly indicated certain
differences in the English and the American nomenclature of some simple
compounds of the Group VB elements. These differences were removed
shortly afterwards, but some years later the chemists of both countries
united in the adoption of a comprehensive system of nomenclature for
phosphorus compounds which was so extensive and often so involved
that only the names of the more common compounds have come into
Prcfncc. xi
wide use. It covered, moreover, only compounds containing one phos-
phorus atom, and the promised extension of this remarkable system to
compounds containing two or more phosphorus atoms has never
appeared. It does not, of course, affect the names of cyclic compounds
and appears in this book only in loyal application to the names of various
reagents used in the synthetic work.
Many of the earlier volumes in the Heterocyclic Series have had
complete tables of all known members of each type of compound,
together with melting points, yields, etc. The adoption of this practice
in the present work would have taken up much space : such tables have,
therefore, been strictly limited both in number and in size. On the other
hand, the melting points of most compounds are given immediately
after their first mention in the text: apart from the reference value of
these constants, they indicate immediately to the reader whether the
compound is solid or liquid at room temperature.
During recent years there has been an increasing tendency in the
larger chemical volumes, reviews, reports, etc., to amplify the text
solely by reference numbers, usually as small superscripts, leaving the
reader, who may want to know when and by whom (and even where)
the work was done, to grope through the distant pages to the complete
references. When this practice is allied to a text that consists almost
solely of a series of rather brief factual statements, the printed page can
have a rather dreary, sterile, and utterly impersonal atmosphere, well
calculated to subdue, if not to kill, the reader’s interest. The result is
that most students, junior and senior, now use a chemical book almost
solely to check individual facts, and only rarely to read. I have tried to
write the present book with sufficient detail to ensure that, without in
any way diminishing its value as a book of reference, whole passages
may actually be read by those to whom the substance of the passage
has some interest. I have also tried to give some human interest to the
material by citing the names of authors, though frequently in parentheses
for brevity. Each of the four Parts is followed by its own list of references,
which are therefore readily available as a comprehensive whole.
All references to papers in languages unfamiliar to most American
and Western European chemists, and all patent specifications, are
accompanied by their Chmical Abstrmts references.
Whilst writing this book, I have been repeatedly and deeply indebted
to Robert S. Cahn for so patiently and so clearly answering my
Dr.
many collections of queries regarding nomenclature. The last Supplement
to the Ring Index covers the field up to 1963 : since then a steady stream
of new heterocyclic compounds, tending to be of increasing complexity,
has been recorded. I am singularly fortunate in having the help and
xii Prcfiirc
advice of so great an authority on nomenclature as Dr. Cahn, to whom
I tender my warmest thanks. If this book enables many chemists to get
a clear and accurate knowledge of the names of these Group VB hetero-
cyclic rings, they will be indebted primarily to Dr. Cahn. It must be
emphasized, however, that I am entirely responsible for any emors in
nomenclature that may still remain.
I wish also to thank Dr. Arnold Weissberger, the Editor of this
Series, both for the patience with which over a very long period he bore
my many delays in starting this book, and for the help and advice he
gave me when at last I had sufficient time to undertake this task.
I must also thank Dr. Reinhard Schmutzler who, whilst I was fully
engaged in writing, kept a sharp look-out through a wide range of
chemical journals for papers dealing with my subjects, and then ensured
that I received a reprint or a copy of them. Without this aid I should have
missed a number of recent and important papers.
I am also much indebted to Professor Lord Todd for the excellent
facilities for compilation and writing which he kindly provided for me
in the University of Cambridge Chemical Laboratory and which I have
greatly appreciated.
It would be difficult adequately to express my thanks to my wife
for all the help which she has given me during the progress of this book,
a progress which at times would have seemed slow indeed without her
cheerful encouragement.
A book of this size, although carefully checked and scrutinized, must
suffer from some errors and omissions. I should be grateful if readers
would notify me of any such faults that they may detect.
F. G. MANN