Table Of ContentORGANOSILICON HETEROPOLYMERS
AND HETEROCOMPOUNDS
MONOGRAPHS IN INORGANIC CHEMISTRY
Editor: Eugene G. Rochow
Department of Chemistry, Harvard University
I. I. Vol'nov-Peroxides, Superoxides, and Ozonides of Alkaline
Earth Metals-1966
M. Tsutsui, M. N. Levy, A. Nakamura, M. Ichikawa, and K. Mori
Introduction to Metal IT-Complex Chemistry-1970
S. N. Borisov, M. G. Voronkov, and E. Va. Lukevits-Organosilicon
Heteropolymers and Heterocompounds-1970
ORGANOSILICON
HETEROPOLYMERS AND
HETEROCOMPOUNDS
s.
N. Borisov
Director, Laboratory of Elastomer Synthesis
All-Union Synthetic Rubber Research Institute
Leningrad
M. G. Voronkov
Director, Laboratory of Heteroorganic Compounds
Institute of Organic Synthesis
Academy of Sciences of the Latvian SSR, Riga
E. Va. Lukevits
Group Leader, Laboratory of Heteroorganic Compounds
Institute of Organic Synthesis
Academy of Sciences of the Latvian SSR, Riga
Translated from Russian by
C. Nigel Turton and Tatiana I. Turton
<±>PLENUM PRESS • NEW YORK • 1970
Sergei Nikolaevich Borisov (1928-1967) was head of the section on heat-resistant
elastomers and director of the Laboratory of Elastomer Synthesis, All-Union
Synthetic Rubber Research Institute, Leningrad. A graduate student at Leningrad
University from 1953 to 1956, in 1958 he defended his Candidate's dissertation
on conjugated hydrogenation-halogenation of organosilicon compounds. He was
the author of more than 50 articles and reviews on the chemistry and physics
of organosilicon, organometallic, and high-molecular compounds and held a num
ber of patents in these fields. Dr. Borisov drowned accidentally on August 6, 1967.
Mikhail Crigor'evich Voronkov was born in 1921. In 1947 he defended his Candi
date's dissertation on the action of sulfur on unsaturated compounds. From 1947
to 1954 he was senior scientist of the Organic Chemistry Department, Faculty of
Chemistry, Leningrad University. In 1954 he transferred to the Institute of Silicate
Chemistry, Academy of Sciences of the USSR, where he worked as senior scientist,
and in 1959 he became director of the Inorganic Polymer Laboratory. In 1961 he
went to Riga, where he set up the Laboratory of Heteroorganic Compounds,
Institute of Organic Synthesis, Academy of Sciences of the Latvian SSR, which he
presently directs. In 1961 he was also awarded the degree of Doctor of Chemical
Sciences for his work on the heterolytic cleavage of the siloxane bond. With E. Ya.
Lukevits Dr. Voronkov is author of Organic Insertion Reactions of Croup IV
Elements (Consultants Bureau, 1966).
Edmund Yanovich Lukevits was born in 1936. In 1966 he defended his Candidate's
dissertation on organosilicon derivatives of furan. He currently directs a group of
laboratories devoted to the study of heteroorganic compounds in the Institute of
Organic Synthesis, Academy of Sciences of the Latvian SSR, Riga.
KREMNEELEMENTOORGANICHESKIE SOEDINENIYA
KPEMHE3HEMEHTOOprAHHQECKHE COElHHEHHH
C. H. SOPHCOB, M. r. BOPOHKOB, 3. H. HYKeBHD
ISBN-13: 978-1-4615-8629-6 e-ISBN-13: 978-1-4615-8627-2
001: 10.1007/978-1-4615-8627-2
Library of Congress Catalog Card Number 68-13393
SBN 306-30379-5
The orginal Russian text, first published by Khimiya Press in leningrad in 1966,
has been corrected by the authors for this edition. The present translation is pub
lished under an agreement with Mezhdunarodnaya Kniga,
the Soviet book export agency.
© 1970 Plenum Press, New York
Softcover reprint of the hardcover 15t edition 1970
A Division of Plenum Publishing Corporation
227 West 17th Street, New York, N. Y. 10011
Distributed in Europe by Heyden & Son Ltd.
Spectrum House, Alderton Crescent, London N.WA, England
All rights reserved
No part of this publication may be reproduced in any form
without written permission from the publisher.
Foreword
There are numerous criteria for measuring the growth and
development of branches of chemistry. This valuable book illustrates
a particular aspect of the growth of organosilicon chemistry. The
extent of this field has developed so greatly in recent years that it
now is desirable to reclassify parts to bring together hitherto frag
mented and relatively disparate sections.
This has been accomplished by the presently available large
units which have been deSignated as "organosilicon heterocompounds."
Simplified expressions of such classification are structural units
of the general type C - Si - heteroelement and heteroelement-C - Si,
in which there are attached to the organosilicon moiety elements
such as oxygen, nitrogen, metals, etc. This arrangement per
mits the correlation of extensive material, which will be invalu
able to chemists in many areas, both in and out of organosili-
con chemistry. Because of the wealth of information, the authors
are currently engaged in the preparation of companion volumes
arranged on this general principle. The scope is broad, and
includes material which will prove highly interesting and useful to
those in academic, industrial, and governmental circles. There is
not only a wide coverage of the literature generally, but the listings
of patent references and of general reviews and books are among
the most complete so far presented.
The authors have a special competence for a work of this kind,
not only because of their active research contributions but also
because of their skill and experience in writing such books or trea
tises. It is Significant to note that some of the outstanding books in
organosilicon chemistry have come from eastern European countries.
An appropriate illustration is the classic on "Organosilicon Com
pounds," the three-volume work in English by Bazant, Chvalovsky,
and Rathousky. This raises a question on the "Literature Cited"
section of the present volume. After the magnificent subsection of
v
vi FOREWORD
"Monographs, Reviews, and Dissertations," there comes "Articles
and Reports of Russian Authors." These comprise about 30% of the
total references, the remainder being "Articles and Reports of For
eign Authors." It is, of course, most helpful to have a full coverage
of the continuously important and significant studies in this area by
Soviet chemists. However, with the current awareness of chemists
generally of such contributions, thanks in part to English editions of
many Soviet research publications, there appears little to commend
the segregation of the common, interdependent interests and studies
which are international in scope.
This new series promises to assume classic proportions in
the area of organosilicon chemistry. As a corollary of the growth
of this segment of chemistry it may indicate to some, if the marked
development continues, the possible need for a periodical on orga
nosilicon chemistry. This, as well as one on transition-metal orga
nometallic chemistry, was mentioned several years ago. At this
stage, however, one is hardly prepared to state that such specializa
tion would be a happy development.
Ames, Iowa
Henry Gilman
January 20, 1970
Preface to the English Edition
We are pleased that Plenum Press has selected our book as
one of the Soviet monographs on the chemistry of heteroorganic
compounds being made available to English readers. The list of re
ferences at the end of the book shows that about 70% of the material
examined was published outside the USSR. We therefore hope that,
on the one hand, the English translation will considerably enlarge the
number of readers of the book and, on the other, will give foreign
scientists a more complete picture of the work of Soviet authors on
the chemistry of organosilicon heterocompounds, which takes up ap
proximately 30% of the bibliography. Ultimately, this may further
the progress of this rapidly expanding branch of chemistry, which is
of interest from both the theoretical and the practical points of view.
We based the arrangement of the material in the book mainly
on the extent to which a certain class of compounds was character
istic of the elements of the given group. Therefore, starting with
Chapter 3, we went from compounds with Si-O-M bonds to Si-C-M,
Si-N-M, and finally, Si-M bonds. In Chapter 2 we deliberately
placed compounds of the type Si-M second in the series. In discuss
ing compounds of Group I elements, we placed Si - M compounds first,
while compounds with Si-O-M bonds are examined after deriva
tives containing nitrogen.
In conclusion we would like to thank all the Soviet and foreign
scientists who sent us favorable and critical comments on the Rus
sian edition of our monograph. We are particularly grateful to Pro
fessor Henry Gilman for his interest in the English edition of this
work, and to Professor Eugene Rochow for having kindly agreed to
the inclusion of this volume in the series Monographs in Inorganic
Chemistry published by Plenum Press.
Riga, July 1969 M. G. V., E. Ya. L.
vii
Preface to the Russian Edition
The marked difference between compounds of silicon and the
analogous compounds of its upper neighbor in the periodic system,
carbon, their exceptional practical value, and the vast number of the
oretical and applied investigations of a wide range of problems in the
chemistry and technology of organic and pseudoorganic compounds of
this element have led to the appearance of a new and independent field
of chemical science - organosilicon chemistry. It is concerned with
practically all the nonsilicate compounds of silicon.
In the last two decades the chemistry of organosilicon com
pounds has developed particularly vigorously. Many countries have
experienced the development of high-tonnage industrial production of
a wide range of organosilicon monomers, liquids, resins, elastomers,
and all kinds of materials based on them. As a result, in recent years
a large number of monographs, reviews, and textbooks on general
and particular, theoretical and applied problems in organosilicon
chemistry have been published.
The establishment and independent development of organosili
con chemistry is a clear example of the general dialectic process of
differentiation and integration of contemporary science, which is
characteristic of our epoch. However, not all sections of the nonsil
icate chemistry of silicon have developed equally. Thus, while in
the middle of the present century investigations were concentrated
predominantly in the region of polyorganosiloxanes and the mono
mers required to prepare them, in the sixties there has been a sharp
increase in the attention paid to organosilicon heterocompounds con
taining nitrogen or inorganic elements. As a result a new disci
pline has developed - the chemistry of organosilicon heterocom
pounds - a peculiar border zone which closely adjoins and is
deeply rooted in the classical divisions of heteroorganic, and or
ganic, chemistry. However, in the literature on the chemistry of
viii
PREFACE TO THE RUSSIAN EDITION ix
organosilicon heterocompounds there has been little work as yet
by way of generalizing and systematizing progress.
In the well-known monographs on organosilicon chemistry
[4, 78, 83, 85, 110] and also in books and reviews on organic com
pounds of Group IV elements [100, 105, 112, 117] at best only a
few pages are devoted to monomeric organosilicon heterocompounds.
The first and still the most complete review of this field is Bori
sov's article [19]. However, the derivatives of alkali metals and
elements of the sulfur subgroup are not examined in thil? article.
This gap has been partly filled by two reviews by Gilman and his
co-workers [92, 125] of organosilicon compounds containing an al
kali metal atom attached directly to a silicon atom. A recent short
article by Wiberg and his co-workers [123] merely generalized the
results of several dissertation studies of the chemistry of silyls of
some Group II-IV metals.* The individual subjects of the review
[19] were subsequently supplemented by new communications de
scribing monomeric siloxy derivatives of metals [60, 101, 114],
cyclic silicon compounds containing atoms of other elements [9],
and also silylamides of alkali metals and reactions involving them
which lead to the formation of heterosilane compounds [121, 122].
These publications, which are brief and limited with respect to the
range of the classes of compound examined, constitute the whole of
the review literature in the field of organosilicon heterocompounds.
Polymeric organosilicon heterocompounds, particularly poly
heterosiloxanes (polymers built up from the alternating groups -
Si - 0-M - 0-) are discussed in a much greater number of reviews
[4, 5, 6, 8, 10,11,36-39,43, 73a, 75, 77, 79;--81, 92, 99, 102, 108,
110,12·0]. However, as a rule, there is a far from exhaustive de
scription of the individual types of heterosiloxane polymers or a
brief list of known types without details. The most complete publi
cations in this field are those of K. A. Andrianov [6,8] and J. Jones
[102], but they only cover material published up to 1962. Up to
now, no single review has appeared in the literature which classi
fies work on organosilicon compounds containing elements of the
sulfur subgroup or the silicon-oxygen-alkali metal bond.
• Data on the synthesis and properties of compounds with Si - M bonds (M is not an alka
li metal) are also given in a review published in August, 1966 [28a].
x PREFACE TO THE RUSSIAN EDITION
From this account it is clear that all available material on
organosilicon heterocompounds, which is scattered, incomplete,
and largely out-of-date, does not give a single clear systematic
idea of the diversity and peculiarity of this exceptionally interesting
new section of chemical science. This compelled us to attempt to
examine systematically the contemporary state of organosilicon
heterochemistry as fully and as up-to-date as possible.
The book gives quite a detailed account of preparation meth
ods, physical and chemical properties, analysis methods, and the
possibilities of the practical application of monomeric and poly
meric organosilicon derivatives of inorganic elements. There are
also discussions of theoretical problems connected with the struc
ture and reactivity of heteroorganic and pseudoorganic derivatives
of silicon. It is proposed to continue the examination of these prob
lems later in monographs on the chemistry of organosilicon deri
vatives of the organogens phosphorus and sulfur and also nitrogen.
The book is based on as exhaustive a coverage of the litera
ture data as possible and the authors' own investigations, published
mainly up to May 1, 1965. Chapters 2 (apart from section 3.1), 3,
4,5, 7, and 8 and sections 6 (Ch. 1) and 2 (Ch. 6) were written by
S. N. Borisov and M. G. Voronkov. Chapter 1 and sections 3.1 (Ch. 2)
and 1 (Ch. 6)were written by E. Ya. Lukevits and M. G. Voronkov.
In writing the monograph the authors were guided by the ter
minology in the proposed scheme for the nomenclature of organosili
con compounds [62] and the recommendations of the chemical no
menclature section of the Eighth Mendeleev Conference on General
and Applied Chemistry.
The authors are grateful to all the many Soviet and foreign
scientists who supported the work on this book with their practical
help, unquenchable interest, and valuable advice. We are also grateful
to those who helped us to prepare the manuscript for publication.
All critical comments and suggestions will be gratefully re
ceived and will help us in work on the next books of this series.
S. N. Borisov, M. G. Voronkov, and E. Ya. Lukevits
Leningr ad - Riga
March 1966
