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Book Review The Chemistry of the Allenes. Edited by S. R. Landor

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thane in good yield. A similar increase in activity was observed when using triethylsilane (run 7), which furnished
only hexaethyldisiloxane as oxidation product[’]. On the
other hand, a batch reaction revealed decreased catalyst
efficiency in terms of conversion of 1, although a much
higher production of higher siloxanes (run 6) was noted, in
a ratio similar to that obtained under flow conditions.
In order to pinpoint the origin of the component atoms
in the methane formed, as well as that of the oxygen in the
siloxanes, several labeling experiments were performed.
Execution of run 5 (Table 1) with DZ instead of H2 gave
mainly CD4 (84%) in addition to some protic (predominantly CH3D) methane. None of the silicon-containing
products (and 1) showed incorporation of deuterium. Similarly, use of 13C0gave mainly 13CH4(84.4%) and revealed
the absence of I3C in the other product molecules. Thus,
clearly, the major contributors to methane formation are
CO and H1,minor amounts arising from 1 and siloxane
decomposition or as part of the pathways which lead to
higher siloxanes.
Since it was of interest whether the oxygen in the siloxane product was, in fact, somehow derived from the kieselguhr support or other oxygen sources, an additional control was carried out involving Cl’O. This experiment revealed completely clean incorporation of “ 0 into all isolated siloxanes.
Mechanistically, it is tempting to formulate surface
pathways analogous to those found in the Fischer-Tropsch
reaction“’], involving not only CO and H-H, but also
Si-Si and Si-C activation on the nickel surface. Current
work is directed at further mechanistic elucidation of the
pathways controling these unprecedented transformations
and at finding other substrates for the carbon left after it
has been stripped of its oxygen by 1.
Received: March 5, 1984 [ Z 738 IE]
German version: Angew. Chem. 96 (1984) 449
[l] E. Colvin: Silicon in Organic Synrheris. Butterworths, London 1981.
121 a) C. Eaborn, Organosilicon Comlmmds, Academic Press, New York
1960; b) S . Murai, N. Sonoda, Angew. Chem. 91 (1979) 896; Angew.
Chem. Int. Ed. Eng1. 18 (1979) 837; c) K. C. Brinkman, J. A. Gladysz,
OrganometaNics 3 (1984) 147, and references cited therein: d) K. Tamao,
N. Ishida, T. Tanaka, M. Kamada, ihid. 2 (1983) 1694.
131 1. S. Alnaimi, W. P. Weber, Organometa//ic.$2 (1983) 903 and references
cited therein.
[4] Cf. K. Tamao, M. Akita, R. Kanalani, N. Ishida, M. Kumada, J. Organomef. Chem. 226 (1982) CY; T. J. Groshens, K. J . Klabunde, OrganomefaNics 1 (1982) 564; E. Colomer, I<.J. P. Corriu, C. Marzin, A. Vioux,
Inorg. Chem. 21 (1982) 368; G . SiiO-Fink, Angew. Chem. 94 (i982) 72;
Angew. Chem. Int. Ed. Engl. 21 (1982) 73: Angew. Chem. Suppl. 1982,
71; M.-J. Fernandez, P. M. Maitlis, J . Chem. Soc. Chem. Commun. 1982,
310.
[5] A curious rate acceleration of the transition metal-catalyzed reduction
of carbon monoxide by hydrogen in the presence of hydrosilanes has
been reported: L. Kaplan, OrganometaNics 1 (1982) 1102.
161 W. NO11: Chemistry and Techno1ug.v .f Silicones, Academic Press, New
York 1968. B. Arkles, CHEMTECH 1Y83, 542.
[7] M. D. Curtis, P. S . Epstein, Adu. Organornet. Chem. 19 (1981) 213.
[S] 1. M. T. Davidson, A. V. Howard, J. Chem. Sac. Faraday Trans. 1 1 9 7 s .
69.
[Y] There are indications that the Et- Si bond is oxidatively cleaved more
slowly than the Me-Si bond: L. Spialter, D. J. Austin, Inorg. Chem. 5
(1966) 1975.
[lo] C. K. Rofer-DePorter, Chem. Reu. 81 (1981) 447.
BOOK R E V I E W S
The Chemistry of the Allenes. Edited by S. R. Landor. Academic Press, London 1982. Vol. 1: Synthesis, p. 1-234,
bound, $ 66.00; Vol. 2: Reactions, p. 235-578, bound,
$ 86.00; Vol. 3: Stereochemical, Spectroscopic and Special Aspects, p. 579-882, bound, $ 86.00. Each volume
contains index to whole work (pp. 26).
The subjects of all three volumes are presented in a short
introduction (Chapter 1, 17 pp.) in Volume 1 by S . R.
Landor. The remainder of the first volume is devoted to P.
D. Landor’s description of allene synthesis. Chapter 2
deals with the synthetic methods for the hydrocarbons, for
halogenated allenes, then for allenes containing alcohol,
ether, aldehyde, ketene, carboxylic acid and carboxylic
acid derivative functions, and finally for allenes bearing
heteroelements (B, Si, Sn, N, P, S, Se, Te). The shorter,
third chapter covers the synthesis of allenes containing additional olefinic, acetylenic or allenic functions. Each class
of substance is dealt with in a separate section with an independent reference list. It is here that the need for an additional author index (with reference number and page
number) becomes apparent, with which to keep track of allenes with several functional groups and to keep a better
check on the comprehensiveness of the literature citations.
This applies not only to this volume devoted to synthesis,
but to the whole series, since a complete author index allows the rapid tracking down of a whole range of publications which describe not just the synthesis of allene derivaAngew. Chem. I n t . Ed. Engl. 23 (1984) No. 6
tives but also their reactivities and/or other properties.
Random sampling of the synthesis volume revealed that
the literature citations (up to 1980), though not comprehensive, d o at least cover the most important literature.
The text does not reveal whether comprehensiveness or a
review of the most important methods was the intention.
Nor are the somewhat older but excellent reviews of various aspects of allene chemistry referred to. In the interests
of a clearer conspectus the reviewer would like to have
seen a distinction made in the various sections between
reactions in which allenes merely undergo transformations
without the cumulene being affected or altered and syntheses where the cumulene is actually created. A classification according to mechanism would have been preferable
to the formal one used: For instance, Section 2.3.1 o n the
synthesis of allenic alcohols (“Reduction Methods”) deals
with the addition of hydride ions to 1,3-enynes, the addition of a hydride ion to the carbonyl group of allenic ketones and the nucleophilic substitution (SN2’) of halogen
atoms in the propargyl position by hydride ions, while in
Section 2.3.4 (“Use of Organometallic Reagents”) the reaction of allenic Grignard reagents with ketones, of Grignard
reagents with allenic ketones, and the fragmentation of tosyl hydrazones by butyllithium are discussed as well as the
reaction of organometallic compounds with propargyl halides and suitable epoxides. The addition of organometallic
compounds to 1,3-enynes is dealt with separately in Sec46 1
tion 2.3.3. The hydroxyalkylation of an allene ether with
butyllithium and 3-pentanone described at the end of this
section does not belong here. This criticism, however, applies only to the arrangement and not to the content. The
author has presented the methods scientifically correctly
and has also given a critical indication of the limits and applicability of the methods.
S . R . Landor covers the substitution reactions of 1- or 3-,
4-, and 5-halo-1,2-alkadienes in Chapter 4 (Volume 2). The
most interesting reactions are those of the I-halogen derivatives with geminal hydrogen atoms, since these can yield
allenic carbenes by 1,l-elimination under the influence of
strong bases. These carbenes can react with nucleophiles
by undergoing 1,l- or 1,3-addition or are captured by olefins (see also Section 2.1.1, c) with the formation of allenylidenecyclopropanes. After the relatively short but informative report by H. Hopf on sigmatropic rearrangements
of stable allenes, T. L. Jacobs discusses the transition metal
complexes of the allenes. A list with literature citations
and commentaries makes possible a rapid overview of the
allenic complexes that have so far been isolated; then follows a discussion of their synthesis, structure and stereochemistry. The oligomerization and polymerization reactions of the metal complexes described at the end should
be of interest to organic chemists, too. It can be seen from
the reference list that this is a very new field; most of the
references appeared in the 1970s, the majority of them towards the end of the decade. Chapter 5 (Volume 2) summarizes practically all the types of allene additions and cycloadditions: First S . R . Landor reports briefly on reactions with carbenes, which lead to a wide range of interesting cyclopropanes, and then on the nucleophilic addition
of hydride ions and organometallic compounds. After a
short section on radical additions T. L. Jacobs presents the
large field of electrophilic additions. The tables which
summarize the reactions with protonic acids, sulfenyl chlorides, halogens and with mercury salts are very useful for
gaining a preliminary overview. These are followed by the
mechanistically interesting epoxidation reactions; the methyleneoxiranes formed initially are only isolable with
bulky residues. The last three sections of Chapter 5 contain
a survey of allene cycloadditions. While the number of
reactions with 1,3-dipoles is relatively limited (S. R. Landor), [2 2]-cycloadditions seem of greater importance. Their
preparative and mechanistic development between 1970
and 1979 is described by H. Hopf; he cites reviews on earlier work. In the section on [4 2]-cycloadditions he points
out that vinyl-substituted allenes and bisallenes react as
dienes, while simple allenes function as dienophiles.
Chapter 6 in Volume 3, concerning the stereochemistry
of allenes, is particularly worthy of mention. In it W.
Runge first of all explains the phenomenon of allene chirality, then takes up the synthesis of chiral allenes, and finally mentions some chosen reactions whose course is influenced by configuration. However, instead of retaining
the confusing cis and trans nomenclature for some of the
trisubstituted olefins the author should have adopted the
E / Z nomenclature. In Chapter 7 S. R . Landor informs in a
lively manner about all the naturally occurring allenes so
far isolated and about the successful and unsuccessful attempts at their synthesis. A . Claesson discusses the known
biologically active allenes in Chapter 8 (93 references). In
Chapter 9 entitled “Allenic Intermediates in Organic Synthesis”, A . Claesson and L.-J. Olsson describe the reactions
of stable and also unstable allenes only appearing as reaction intermediates, from the point of view of the type of
compound synthesizable. Thematically this section would
fit better into the second volume where a large proportion
of the reactions are already described. Chapter 10, written
by W . Runge and concerning spectroscopic properties,
ought to be of great value to spectroscopically inclined
synthetic chemists; here at last is a good collection of UV,
IR, photoelectron, NMR and mass spectroscopic data, in
contrast to books concerning spectroscopic methods in organic chemistry,, where the allenes are usually shortchanged. In the last, very brief chapter P. D. Landor reports on the methods of synthesis of nine specialized, variously functionalized allenes ; an expansion of this section
would have been desirable.
This three volume monograph is very readable, because
the text is copiously illustrated with structural formulas.
The typesetting of the text and formulas is very good and,
apart from a few unimportant exceptions that were perhaps unavoidable in a first edition, free from errors. The
great value of this work is based on two facts: The individual sections are written by leading specialists and, for the
first time, a complete picture is given of practically every
aspect of allene chemistry. (The whole thing ought to have
been published as one volume, which would undoubtedly
have lowered the price.)
Even taking into account the small imperfections mentioned here, this monograph, consisting of three books
can be warmly recommended to all who are concerned
with or wish to be concerned with the chemistry of allenes
and who require a comprehensive overview. The high
price will certainly prevent many people from acquiring a personal copy; however, it ought to be available in
departmental libraries to ensure its accessibility to undergraduates and graduate students alike. This work offers the
specialist a solid basis, which covers all significant publications up to 1980 and from which he can research the literature of the last few years for himself. This is very necessary because we are at present in a phase of rapid development in the field of allene chemistry.
Gerhard Himbert [NB 613 IE]
Fachbereich Chemie der
Universitat Kaiserslautern
+
+
462
Encyclopaedia of the Terpenoids. Vol. 1: A-H, Vol. 2: IZ. By J . S . Glasby. John Wiley, Chichester 1982. 2646
pp., bound, L 250.00.
The systematic coverage of the vast field of naturally occurring terpene derivatives is, without doubt, a very useful
and urgent task, particularly since the work by Deuon and
Scott only covers the literature up to 1971. The present
comprehensive summary unfortunately only covers the literature up to the end of‘ 1979, but nevertheless includes
more than 10000 compounds. It is, however, questionable
whether all the substances included belong here, since substances such as thelepine, for example, are included although it can scarcely be described as a terpenoid. (Thelepine is 3’,5‘,7-bromo-5-hydroxymethyl-2-spiro[benzofuran2(3H),l‘-cyclohexa-2’,5’-diene]-4’-one.) Furthermore, the
indole alkaloids are also regarded as terpenoids, which is
perhaps defensible on the grounds of their biogenesis from
loganine, even though it does not seem very useful.
Neither does the inclusion of substances whose structure is
completely unknown seem to serve any useful purpose.
The formulas are very clearly presented and great care
has been taken in the indication of stereochemistry. There
Angew. Chem.
Inf. Ed. Engl. 23 (1984) No. 6
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