The Nitrile Oxides: Versatile Tools of Theoretical and Preparative Chemistry

249 Pages·1971·6.679 MB·English

by  Christoph Grundmann, Paolo Grünanger (auth.)

Organische Chemie in Einze1darstellungen
Band 13
Herausgegeben von
Hellmut Bredereck . Klaus Hafner
Eugen Miiller
Ch. Grundmann . P. Griinanger
The Nitrile Oxides
Versatile Tools of Theoretical
and Preparative Chemistry
Springer-Verlag Berlin· Heidelberg. New York 1971
ChristophGrundmann, Carnegie-Mellon University, Pittsburgh, PA., USA
Paolo Grilnanger, Universita di Pavia, Pavia, Italy
ISBN-13: 978-3-642-99993-2 e-ISBN-13: 978-3-642-99991-8
DOl: 10.1007/978-3-642-99991-8
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Softcover reprint of the hardcover 1s t edition 1971
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Preface
From their discovery in the last decade of the nineteenth century on,
the nitrile oxides comprised a rather small group of little-known and
little-investigated unstable organic derivatives of hydroxylamine. Around
1950, the astonishingly wide variety of their reactions started to become
gradually unveiled. This reactivity has made them increasingly important
as valuable tools for many syntheses. Simultaneously, the newly dis
covered transformations raised interesting theoretical questions and their
pursuit has generally enriched our understanding of reaction mechanisms
of organic chemistry.
At the same time, when nitrile oxides finally had won on their
own a position of justified interest in the eyes of the organic chemist,
came the discovery that fulminic acid, was in fact the parent member of
this series. Thus, suddenly the nitrile oxides had acquired the most
illustrious ancestry. Fulminic acid was discovered in 1800, at the dawn
of modern chemistry, and since then the riddle of its true structure as
well as the proteus-like variability of the molecule in its multitude of re
actions has at one time or another attracted some of the most brilliant
minds of organic chemistry, among them Berthollet, Gay-Lussac, Liebig,
Wohler, Berzelius, Gerhardt, KekuTe, Griess, Armstrong, Holleman, Scholl,
Nef, H. Wieland.
The present authors readily confess that they too have succumbed
to the fascination obviously emanating from the longest-known member
as well as from the younger offspring of the nitrile oxide family. To
their surprise, no review of this field has been attempted since Wieland's
monograph of 1909, which covered mainly fulminic acid. One of the
authors has recently published an article on the preparative aspects of
nitrile oxides and a short review of their chemistry. The unexpectedly
wide interest that these publications have found among chemists and
members of related sciences has encouraged authors and publisher alike
to present this monograph as the first comprehensive survey of this
area.
The authors did not strive to achieve handbook-like coverage and
neutrality. The reader will find the authors' own experience in this field
reflected in the elimination of reports of only historical interest or of an
VI Preface
erroneous nature, in sometimes critical interpretation of existing data,
and in the occasional addition of unpublished facts from their laboratories.
A great help and stimulation for the undersigned has been advice,
discussion, and contributions of unpublished data by a number of
distinguished colleagues, among them J. Armand, W. Beck, P. Beltrame,
A. Dondoni, F. Eloy, R. Huisgen, A. Quilico, A. Ricca, P. v. R. Schleyer and
G. Speroni to whom the authors extend their sincere gratitude.
Christoph Grundmann
Pittsburgh and Pavia, January 1971 Paolo Grilnanger
Contents
Chapter I: Introduction . . . . 1
A. Definition, Nomenclature. 1
B. History ........ . 3
C. General Properties . . . . 10
Chapter II: Physical Properties . 15
A. General ..... . 15
B. Electronic Spectra . 24
Chapter III: Preparation 31
A. General ..... . 31
B. Formonitrile Oxide (Fulminic Acid) and Derivatives 33
C. Other Nitrile Oxides . . . . . 44
1. From Aldoximes. . . . . . 44
2. From Primary Nitroparaffins 51
3. From Fulminates . . . . . 54
D. Preparation in situ . . . . . . 55
E. Functional Groups in Nitrile Oxides 58
Chapter IV: Chemical Reactions Involving Only the Nitrile Oxide 62
A. Isomerization to Isocyanates . 62
B. Deoxygenation to Nitriles. . . . . 68
C. Polymerization . . . . . . . . . 69
1. Polymerization of Fulminic Acid. 69
2. Polymerization of Other Nitrile Oxides 75
Chapter V: Addition Reactions Leading to Cyclic Structures:
1,3-Dipolar Cycloadditions. . . . . 85
A. General. . . . . . . . . . . . 86
B. Reactions with C=C Derivatives. 96
C. Reactions with C=C Derivatives. 112
D. Reactions with C=O and C=S Compounds "120
E. Reactions with C=N Compounds . . . . 125
F. Reactions with Nitriles . . . . . . . . . 130
G. Reactions with Other Unsaturated Systems 133
VIII Contents
Chapter VI: Addition Reactions Leading to Open-Chain Struc-
tures; 1,3-Additions. . . 140
A. General .......... . 140
B. Addition of Hydrogen . . . . 142
C. Addition of Water (Hydrolysis) 143
D. Addition of Alcohols and Phenols 147
E. Addition of Sulfides and Thiols . 148
F. Addition of Inorganic and Organic Acids and their Derivatives 153
G. Addition of Ammonia and its Derivatives. . . . 161
H. Addition of Azide, Cyanide and Thiocyanate Ions 170
I. Addition of Metallo-Organic Compounds . 173
K. Addition of Free Radicals. . . . 175
L. Other Addition Reactions. . . . 176
Chapter VII: Miscellaneous Reactions. 178
Chapter VIII: Physiological Properties and Applications of Nitrile
Oxides . . . . . . . . 184
Chapter IX: Tabular Survey . 188
Subject Index . . . . . . . 234
I. Introduction
A. Definition, Nomenclature
Definition. Nitrile oxides, RCNO, are organic compounds which contain
the monovalent functional group -CNO bound directly to a carbon
atom of the organic moiety of the molecule. Only the first member of
this series, fulminic acid or formonitrile oxide, H-CNO is an exception;
mainly for this reason its chemistry differs in some respects from that of
its homologs.
According to the above definition, the consideration of compounds
which may contain a covalent bond between the -CNO group and an
element other than carbon, e.g.,
(C6Hs)3-Si-CNO or C6Hs-Hg-CNO,1
is not included. As with hydrocyanic acid too, the metal salts and the
numerous transition metal complex salts of fulminic acid are generally
considered part of inorganic chemistry. They will receive only limited
coverage, the more so since it is generally established that the inorganic
chemistry of fulminic acid-quite in contrast to its organic chemistry
parallels closely that of hydrocyanic acid.2, 3 Nitrile oxides as transient
intermediates have been postulated frequently in reaction mechanisms,
especially in reactions leading to 1,2-oxazole (isoxazole) and 1,2,5-oxa
diazole (furazan) derivatives. Such reactions will be discussed in this
book only in cases where unambiguous evidence exists for the occurrence
of nitrile oxides; for a complete coverage reference is made to recent
monographs.4-7
w.:
1 Beck, Angew. Chern. 75, 872 (1963).
w.:
2 Beck, Z. Naturforsch. 17b, 130 (1962).
w.,
3 Beck, lux, F.: Chern. Ber. 95, 1683 (1962).
4 Quilico, A.: The chemistry of heterocyclic compounds (ed. A.Weissberger), vol. XVII,
chap.: Isoxazoles and related compounds, p.I-176. New York: Interscience 1962.
5 Behr, L. c.: The chemistry of heterocyclic compounds (ed. A. Weiss berger), vol.
XVII, chap.: Furazans, p. 283-320. New York: Interscience 1962.
6 Barnes, R.A.: Heterocyclic compounds (ed. R.c. Elderfield), vol. 5, chap.: Isoza
zoles, p. 452-482. New York: J. Wiley & Sons 1957.
7 Boyer, J. H.: Heterocyclic compounds (ed. R. C. Elderfield), vol. 7, chap.: Oxadia
zoles, p. 462-508. New York: J. Wiley & Sons 1961.
2 Introduction
Nomenclature. The nomenclature of nitrile oxides closely follows that
of nitriles, whenever applicable, e. g. when a certain component can be
rationally named to include somewhere in the name the term "nitrile",
this will be followed by "-oxide". There are a number of occasions,
however, where this rule will lead to ambiguity, for instance, when the
molecule contains more than one nitrogen function capable of forming
an N-oxide. In such, and many other cases, a more succinct and less
clumsy name is often arrived at by using the termfulmido for the-CNO
group (derived from fulminic acid, analogous to cyano derived from
hydrocyanic acid).
A comprehensive survey of the chemistry of nitrile oxides has never
been made. Since 1965, a few shorter review articles have appeared, mostly
within the frame of handbooks, stressing either the preparative aspects
or the general chemistry of nitrile oxides.8- 12 None of them covers the
numerous reactions of nitrile oxides as exhaustively as this book.
8 Grundmann, c.: Methoden der organischen Chemie, 4th ed. (ed. E. MUller), vol. 10/3,
chap.: Methoden zur Herstellung und Umwandlung von Nitriloxiden, p.837-870.
Stuttgart: G. Thieme 1965.
9 Grundmann, c.: Chemistry of nitrile oxides. Fortschr. Chern. Forsch. 7, 62-127
(1966).
10 Grundmann, c.: The chemistry of the cyano group (ed. Z. Rappoport), chap.:
Nitrile oxides, p. 791-851. New York: Interscience 1970.
11 Grundmann, c.: Syntheses of heterocyclic compounds with the aid of nitrile oxi
des. Synthesis, 344-359 (1970).
12 Quilico, A.: Advances in nitrile oxides chemistry. Experientia 26, 1169-1183
(1970).
History 3
B. History
Some alchemists and pharmacists during the 17th century, among them
Cornelius Drebbel (1572-1634) and Johann Kunckel von Lowenstern
(1630--1703) have probably known the mercury and silver salts offulminic
acid (formonitrile oxide),l a but from a scientific point of view the history
of nitrile oxides begins really with the description of mercury fulminate
in 1800 by Howard,l as the product of the reaction between ethyl alcohol,
nitric acid and mercury. It is still interesting-and somewhat amusing
too-to note that the British chemist was led to the above combination
not by shear Edisonian curiosity, but by serious theoretical consider
ations.
To translate his reasoning into modern chemical language, what he
wanted to do was to synthesize hydrochloric acid. We must remember
that chlorine, although prepared by Scheele in 1774, was not recognized
as an element until 1810, and its relation to hydrochloric acid was equally
unclear. From the experience with the better known acids, it was believed
that all acids had to contain oxygen (the German name "Sauerstoff" for
oxygen, derived from "sauer"=acidic, still bears witness of this old
belief), and that hydrochloric acid was therefore a combination of hydro
gen, oxygen and the hypothetical element "murium". Chlorine was
consequently considered an oxide of murium. Howard chooses nitric acid
as oxygen donor and alcohol as hydrogen source and continues:
"»ith this in view, I mixed many substances with alcohol and nitric
acid, as I thought might (by predisposing affinity) favor, as well as attract,
an acid combination, oft he hydrogen oft he one, and the oxygen oft he other."
He obtained, however, not mercuric chloride, but the similar looking
mercuric fulminate; when he tried to liberate hydrogen chloride from it
by reaction with concentrated sulfuric acid, he found himself faced to
his uttermost surprise by a violent detonation. His further investigation
led him to believe that mercuric fulminate was a compound composed of
"nitrous etherized gas" (ethyl nitrite), oxalic acid and mercuric oxide.
Not before 1824 did Gay Lussac and Liebig 2 provide the first correct
analysis of silver fulminate. At the same time, Liebig recognized that
potassium hydroxide removed only one half of the metal giving the
complex salt K[Ag(CNOhJ. The same kind of salts were obtained when
silver fulminate was reacted with alkali halogenides. This observations
together with the fact that fulminic acid is formed from ethyl alcohol,
whose nature as a two-carbon compound was early recognized, explain
1a Feldhaus: Nitrocellulose 4,83 (1933). - Kirk-Othmer: Encyclopedia of chemical
technology, vol. 6, p.10. New York: Interscience Encyclopedia 1951.
1 Howard, E.: Phil. Trans. Roy. Soc. London 204 (1800).
2 Liebig, J., Gay-Lussac, J. L.: Ann. Chim. Phys. [2]25,285 (1824).