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Hydrocarbon Thermal Isomerizations. 2nd Edition. By Joseph J. Gajewski

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Angewandte
Books
Chemie
Hydrocarbon Thermal
Isomerizations
2nd Edition. By
Joseph J. Gajewski.
Elsevier Science,
Amsterdam 2003.
440 pp., hardcover
£ 113.00.—ISBN
0-12-273351-7
Nothing in organic chemistry could be
much simpler than this—reactions that
proceed without the involvement of
other reagents, that need no solvents or
catalysts, and in which the atoms present
at the start all reappear in the product,
although with alterations to their bonding. Nevertheless, this apparent simplicity has repeatedly fascinated experimentalists and theoreticians who have
worked on thermal isomerizations of
hydrocarbons, which are reactions par
excellence of sustainable chemistry.
Joseph J. Gajewski!s earlier book
Hydrocarbon Thermal Isomerizations
appeared almost a quarter of a century
ago. The second edition, reviewed
here, has the same title and almost the
same length, and the arrangement of
the contents has not changed significantly. The organization of the book follows the pattern of the formula index of
Chemical Abstracts. Thus, it begins with
the thermal inversion of the methane
tetrahedron, and ends with a chapter
on the thermal isomerization of relatively large hydrocarbon molecules
(from C13H10 to C16H16, which includes
molecules such as [16]annulene and
[2.2]paracyclophane).
Angew. Chem. Int. Ed. 2004, 43, 6025 – 6026
By far the longest chapters are those
dealing with the C6 to C10 hydrocarbons.
Of course, that is no accident, because it
is in this range of carbon numbers that
the greatest variation in types of hydrocarbons is found, and that the most
important reaction types occur so frequently. For larger molecules above
that range, there are scarcely any fundamentally new types of reaction behavior
to add to what has gone before, despite
the clear increase in the variety of structures. The reactions of the C6 hydrocarbons are covered in particular detail,
beginning with C6H4 and the Bergman
cyclization of cis-1,2-diethynylethene to
p-dehydrobenzene, and continuing to
the large subject of C6H6 interconversions (including benzene topomerization). That is followed by the electrocyclization of cis-1,3,5-hexatriene to 1,3cyclohexadiene and the degenerative
rearrangement of 1,2-dimethylenecyclobutane, which is known to have an
important role in the dimerization of
allenes and in the formation of tetramethylene-ethane and of the nonKekul5 structures derived therefrom.
The isomerization of 1,5-hexadiene
is discussed in great detail, which is
appropriate, since the Cope rearrangement of this diolefin is probably the
most important of all hydrocarbon isomerizations. This section, which is one
of the longest in the book, shows especially clearly the extent of the progress
achieved in the last 25 years, as seen in
the highly imaginative work of designing
derivatives to study the stereochemistry
of the reactions, and in the experimental
determination of activation parameters
and the theoretical studies to elucidate
the mechanism of this prototypical
[3,3] sigmatropic rearrangement.
The wealth of data on various allyl
vinyl ethers is also covered in detail,
and although these are not hydrocarbons, the discussion of the thermal isomerization behavior of these compounds, which are so important from a
synthetic viewpoint (the Claisen rearrangement), is certainly valuable in this
context. The C7 hydrocarbons covered
in the next section include benzocyclopropene, tropylidene, norcaradiene, toluene, and isotoluene, to mention just a
few of the most important ones. The C8
systems also belong to the classical
study cases in this field, and here again
www.angewandte.org
many of their rearrangement reactions
are of great practical importance; the
chapter discusses benzocyclobutene, oxylylene, cyclooctatetraene, and the
many other C8H8 hydrocarbons, 1,2divinylcyclobutane, 1,2-diethynylcyclobutane, and 1,2-diethynylcyclobutene.
Impressive evidence of the great progress achieved in filling in the details of
the “isomerization map” is provided by
a scheme that shows all the (CH)10 interconversions. In addition to the many different linking pathways, it also gives
their activation parameters, and the
heats of formation of the various starting and product molecules (measured
experimentally or calculated by a variety of methods).
This book by Gajewski is a mixture
of monograph, reference source, and
data compilation. Putting it together
has demanded as much care and diligence as the experimental studies that
it describes. The book is a product of
the author!s years of painstaking fundamental research aimed at perfection,
and to list the few small omissions or
errors would be a petty exercise.
Instead, he deserves profound thanks
for his dedication and patient work.
Henning Hopf
Institut f%r Organische Chemie
Technische Universit+t Braunschweig
(Germany)
Monograph on Organic Chemistry
DOI: 10.1002/anie.200485222
The Molecular World—Alkenes
and Aromatics
Edited by Peter
Taylor and Michael
Gagan. Royal Society of Chemistry,
Cambridge 2002.
184 pp., softcover
£ 17.50.—ISBN
0-85404-680-1
The Molecular World is an extensive
series of books from the Open Univer-
6 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6025
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