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Book Review Houben-Weyl. Methoden der Organischen Chemie. 4th Edition supplementary volumes. Carbene(oide) Carbine Teil 1 und 2. (Volumes E 19b). Edited by M

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tations of complex structures in terms of chemical twinning
of Anby translational or rotational operations-one
derson’s specialities-again provide new insights.
As a whole, the book discusses a selection of compounds
which spans the whole of inorganic chemistry, from fluorides
to intermetallic phases. At the end one is left with the feeling
that the book could have been much more detailed, especially in the last two chapters. This is not so much a criticism of
the book’s content as of its length, and is an expression of the
desire for a modern treatment of inorganic structures which
would be, as far as possible, complete.
I t is also noticeable that the book appears to have been
started several years ago, and in some places the literature
coverage is out of date. This shortcoming, together with a
few errors, should be corrected in a subsequent edition.
On the other hand there are other parts of the book where
one finds “brand-new” information, e.g. on the new hightemperature superconductors. One must also single out for
special praise the fact that for most of the structures discussed the complete structural parameters are given. This
gives the reader direct access to more advanced studies, and
avoids the often tedious searching out of data.
For beginners the “polyhedral” view of structures may at
first seem strange and difficult. However, after a little practice the consistent projections used (Chapters 2-6) allow one
to recognize correlations quickly. For experienced structural
chemists too, polyhedral models are very important; they
can even be used as a sort of “analog computer” ( H . G. von
Schnering) for “calculating” ideal structures and structural
parameters, as is done frequently in this book.
The book undoubtedly enriches the literature in this field,
and it also motivates the reader to look at structures from
different points of view, to understand them, and to look for
cross-correlations. It is useful both for teaching purposes
and for those engaged in structural chemistry research.
Reinhard Nesper [NB 1029 IE]
Max-Planck-Institut fur Festkorperforschung,
Stuttgart (FRG)
Houben-Weyl. Methoden der Organischen Chemie. 4th Edition, supplementary volumes. Carbene(oide),Carbine, Teil
1 und 2. (Volumes E 19b). Edited by M . Regitz. Thieme,
Stuttgart 1989. Part 1: xxxvi, pp. 1-3021; Part 2: xxi,
pp. 1022-2214; hardcover, DM 2680.00 (subscription
price: DM 2412.00).--ISBN 3-13-219704-1
Whereas previously the main emphasis in Houben-Weyl
was on functional groups and compound classes, the editors
have now also turned their attention to reactive intermediates. A two-volume work on free radicals (E 19a) was followed at the end of 1989 by the present work on carbene(oid)s. which is also in two volumes. As the most recent
monograph on carbenes was published in 1975 (reviews since
then have treated only parts of the topic), a serious information gap had appeared. This shortcoming was especially felt
by the synthetic organic chemist wishing to use carbene(oid)s
as building blocks for synthesizing target molecules. A welcome resource in this respect is now available in the amazingly comprehensive, reliable and up-to-date Houben-Weyl volumes.
The introduction ( W W Schoeller, 56 pages) unfortunately does not succeed in clearly presenting the basic principles
of carbene chemistry. Instead it describes what the theory of
carbenes and their reactions has to offer. The contributions
Angew. Chm?.Inl. Ed. En$ 29 (1990) No. 11
of the theory are treated thoroughly and competently, but
the relationship to experiment is often not adequately covered. For example, the four pages of theory on the 1,4-cycloaddition of carbenes are not accompanied by a single
practical example. Strangely, the authoritative studies by
Bickelhaupt and Mayr are presented as unsuccessful attempts
at 1,4-cycloaddition (p. 34). Schoeller explains the negative
activation energies of some carbene addition reactions as
being due to the formation of x-complexes (p. 16), and in
support of this cites Houk, despite the fact that he is responsible for the much more plausible explanation in terms of
entropy control. Other factual errors are on page 49, where
the protonation of I occurs after the carbene rearrangement
of 11, not before it as stated, and on page 55, where neither
the educts (cycloalkylcarbenes) nor their reaction path b are
given correctly. Although it contains useful information on
the capabilities and limitations of the theory, this article is
not a good “calling card” for the work as a whole.
A chapter on carbynes ( H . Heydt, 36 pages) includes everything that is worth knowing about the R-C: bonding
arrangement, which combines the properties of carbenes and
free radicals. The subject matter ranges from the gas phase
reactions of methylidyne and halocarbynes to the formation
of carbynes from their (transition) metal complexes and by
The entire field of carbene(oid) chemistry is then treated in
about 1800 pages. The subject matter is arranged according
to the substitution patterns of the intermediates. These main
chapters and their authors are as follows: alkylidenecarbenes, alkenylidenecarbenes, etc. (P. Stang, 80 pp.); methylene and alkyl- and dialkylcarbenes (K. P. Zeller, H. Gugel,
171 pp.); cycloalkylcarbenes and cycloalkylidenes (U.-H.
Brinker with J: Arct, J. Backes, W. Erdle, M . Fermann, L. K.
Sydnes, 328 pp.); alkenyl- and alkynylcarbenes ( U . Misslitz,
A . de Meijere, 110 pp.); cycloalkenylcarbenes and cycloalkenylidenes ( H . Diirr, 48 pp.); aryl-, diaryl- and heteroarylcarbenes (C. Wentrup, 198 pp.); acylcarbenes (C. Maas,
388 pp.); silylcarbenes, etc. ( H . Tomioka, 49 pp.); halocarbenes (E. I/: Dehmlov, 166 pp.); oxycarbenes ( H . Heydt, M .
Regitz, 55 pp.); sulfocarbenes (K. Schank, 63 pp.); nitrogensubstituted carbenes ( H . Heydt, M . Regitz, 77 pp.); phosphocarbenes ( H . Heydt, M . Regitz, G. Bertrand, 78 pp.). The
way in which these chapters are subdivided according to
second substituent, complexity, etc. largely prevents overlapping and makes it easy to find a particular carbene without
referring to the subject index. An exception: dihalo- and
trihaloalkylcarbenes appear in the chapter on acylcarbenes,
where they belong according to their oxidation state but not
their reaction properties.
All the chapters show a high level of expert knowledge,
orientated according to the authors’ own fields of research.
A few carbene(oid) types that are of preparative importance
(e.g. dihalocarbenes) are not given as much space as one
would expect, as their reactions are already covered in earlier
volumes of the Houben-Weyl series (e.g. 4/3 on cyclopropanes). However, the cross-references are always supplemented by new knowledge and further developments. As the
preparation of reactive intermediates is necessarily linked to
their further reaction, it is not possible in discussing the
various types of carbenes to stick to the traditional HoubenWeyl scheme of presentation (A. Preparation, B. Reactions).
Where some of the authors have nevertheless tried to do so,
it seems artificial and leads to repetition. The most sensible
arrangement, and also the one most often used, is according
to the co-reactants, thus: “preparation o f . . . in the presence
o f . . _ ”The
_ value of the numerous tables with their detailed
information cannot be too highly praised. Sometimes the
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tables contain even more than their titles claim; for example,
Table 155 (p. 1253) on Wolff rearrangements lists not only
heterocyclic but also polycyclic diazoketones. The retrorearrangement of alkynes to alkylidenecarbenes ( R . E C.
Brown) and their preparative applications ( A . S. Dreiding)
are to be found in Table 29 (pp. 131 -134) but not in the
associated text.
The arrangement according to carbene types is useful
from the standpoint of the synthetic chemist who comes
across a carbene during a retrosynthetic analysis of the molecule in which he is interested, and needs further information
on it. However, it is rather inadequate when one is interested
in the carbene aspects of particular reactions. “How can one
selectively functionalize adamantane by C-H insertion of a
carbene at the I -position?” or “Which carbene(oid)s add
preferentially at the lower (or higher) substituted double
such as these can only be
bond of a diene?”-questions
approached in a laborious way by using the 200-page subject
index, which is arranged in order of increasing complexity
(acyclic, cyclic, bicyclic. . .). Some carbene(oid)s have their
own separate entries, while others appear after the corresponding hydrocarbons. The substitutive nomenclature that
is used exclusively (e.g. “Carboxycyclopropan” rather than
“Cyclopropancarbonsaure”) serves the purpose well, although it corresponds to neither the IUPAC nor the Chemical Abstracts rules. Also the bibliography (1 3 pages) and the
author index (100 pages) often give further help; in the latter
the aristocracy stay together, and even Doering and Schleyer
appear under V!
How d o these volumes measure up to the traditional
virtues of Houben-Weyl? Reliability: It seems to me that
printing errors are more frequent than in earlier volumes,
though many of them are not serious (e.g. wrong column
titles on pages 59-69 and 103-133), some are comical (e.g.
optically acute allenes on p. 51 ; “Cyclopentanten”, p. 1073;
yields quoted in “C, p. 1469) and only a few are misleading
(p. 848: the rate constant for the S T interconversion of
s-’; on p. 878
diphenylcarbene is 3 x lo9 s-’, not 3 x
even a laboratory recipe is given for the wrong product IV).
Without making a detailed search I found twenty errors in
structural formulas (with about ten formulas per page this
gives a rate of only 0.1 YO!).
Of about 350 literature references chosen at random, only six contained minor errors.
This is an excellent result when compared with the quality of
the citations in many original papers. Completeness of coverage: For the period 1977-83 my own (selective) literature
collection contains 227 papers of preparative importance on
cdrbenes; of these, 178 (78 YO)are cited in the work. The only
gap that I noticed in the systematic coverage was that benzocycloalkenylidenes are not dealt with under either the cycloalk(en)ylidenes or the arylcarbenes. Up-to-date-ness: Expressing the cited publications for each year as a percentage
of those in my own literature collection, a maximum of 92 %
is reached for 1987, and the figure for 1988 is still as high as
48%. There are even some references to 1989 papers.
As a penalty for the rapid publication the editors have
occasionally had to resort to “reaction paths of lowest energy” (pp. 22,23). “Aus dieser Sicht miissen auch die Berichte
iiber die [I .4]-Addition eines Triplett-Carbens an einem intermediaren Ylid oder iiber ein Vinylcyclopropan/CycIopenten-Umlagerung ablaufen” (p. 37)-such grammatical liberties are below the standard of Houben-Weyl (and of most
other works).
However, minor defects can have an endearing effect in a
book which is otherwise perfect. These volumes will be enthusiastically received by readers with interests in reactive
intermediates, and will become their primary information
resource. However, it is preparative chemists who will benefit most, as the work will give them a much better overview
of the synthetic potential of the carbene(oid)s and enable
them to use it more effectively.
Wolfgang Kirmse [NB 1076 IE]
Fakultat fur Chemie
der Ruhr-Universitat Bochum (FRG)
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