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Book Review Stereoelectronic Effects in Organic Chemistry. By P. Deslongchamps

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BOOK REVIEWS
Stereoelectronic Effects in Organic Chemistry. By P. Deslongchamps. Pergamon Press, Oxford 1983. xi, 375 pp.,
paperback, L 15.25.
This book constitutes the first volume of the “Organic
Chemistry Series” edited by J. E. Baldwin. It is to be welcomed that an author, who has himself made important
advances in this area, provides a review of stereoelectronic
effects, whose importance has come to be increasingly appreciated in the last few years.
After a somewhat short introduction-there is no general historical synopsis-the second chapter treats in detail
the conformation, formation and hydrolysis of 0,N , and S
acetals. Here the author-and the reviewer-prefers the
explanation involving the concept of anomeric effect and
exo-anomeric effect as stabilizing delocalization of nonbonding electron pairs in cr* orbitals rather than the alternative interpretation as the destabilizing interaction of
nonbonding electron pairs (rabbit ear effect). The oxidation of the acetal C-H bond makes the transition to the
next two main chapters, which treat the conformation, formation and hydrolysis of esters, amides and similar compounds. The author adeptly presents his theory concerning
the formation and decomposition of tetrahedral ortho ester
structures and comments on the results obtained by his
and other groups since the famous report in Tetrahedron
(1975).
The next three chapters are dedicated to stereoelectronic
effects in reactions at saturated and sp2- and sp-unsaturated systems. The reactions discussed include the S,2 and
SN2’ reactions, the rearrangements of secondary and tertiary alcohols with vicinal leaving groups, the WagnerMeerwein rearrangement, the nucleophilic addition at carbony1 and iminium compounds and a$-unsaturated ketones, the reduction of a$-unsaturated carbonyl compounds, E2 and ElcB reactions, the Grob fragmentation,
the addition of electrophiles to enolates and the addition
of nucleophiles to triple bonds. The next chapter, entitled
“Potpourri”, discusses further rearrangements, including
the reaction of ortho esters with Grignard reagents, the intramolecular aldol reaction, the ring opening of p-lactams,
and the dipolar cycloaddition of glycosylnitrones. A new
synthesis by the author’s group of erythronolide A is also
included. In this an intermediate 1,7-dioxaspiro[5.5]undecane was synthesized by the exploitation of stereoelectronic effects. The last chapter deals with such effects in
enzymic reactions. The book is rounded off by comprehensive author and subject indexes.
This monograph is distinguished by its clear organization, precise language and cleanly designed formula diagrams. The author has succeeded in extracting the essential
stereoelectronic aspects from the voluminous literature
and in discussing them pertinently. He presents the work
of his own group just as clearly and develops his theories
therefrom in a factual manner which is easily understood.
The wide range of reactions treated and the plethora of
references at the end of every chapter (over 700 references
in all) make this book an important work of reference for
every chemist or student with an interest in organic chemistry.
B. Bernet [NB 634 IE]
Organisch-chemisches Institut
der Universitat Zurich (Switzerland)
Angew. Chem. Int. Ed. Engl. 23 (1984) No. 9
Pyrolysis: Theory and Industrial Practice. Edited by L. F.
Albright, B. L. Crynes, and W. H . Corcoran. Academic
Press, New York 1983, xviii, 482 pp., bound, $ 65.00.
In 18 chapters several authors principally deal with
the manufacture of ethylene and other olefins, diolefins
and aromatics from various feeds. The carbonization of
solid fuels such as coal, oil shale and biomass for the production of liquid products, the widely utilized coke oven
technology, and the pyrolysis of plastic wastes are only
treated briefly. The coking of heavy oils and tar sands,
which also belongs to the broad area of pyrolysis is not
considered.
The theoretical treatise in the initial chapters is mainly
concerned with the reaction mechanisms of cracking methane through butane and other paraffins and olefins, diolefins, naphthenes and aromatics. Practice leads theory in
cracking mixtures; data on the production of light cracking products from feeds not originating from crude oil
such as coal, tar, shale oil, polyolefins, and biomass are
mainly empirical in nature.
A further theoretical chapter deals with the mathematical modelling of the reactor and the pyrolysis reactions of
hydrocarbon gases, naphtha and gas oils. Sensibly defined
peripheral conditions yield reliable predictions with an acceptable amount of effort.
Coke formation and gasification are of considerable importance in running industrial pyrolysis plants. The treatment of these complex problems reveals the limits of
knowledge in this area. A separate chapter is devoted to
undesirable reactions on the metal surfaces of reactors
such as carbonization, coke formation, and the decomposition of ethylene. Measures for prevention and control are
presented.
The discussion of the theory and application of laboratory reactors to investigate the kinetics of pyrolytic reactions covers the most important types of reactors.
The rest of the book is aimed at those readers who are
mainly interested in the technology and operation of pyrolysis plants for the production of base products for the petrochemical industry. The topics not only include cracking
in tube furnaces as normally used nowadays, together with
the preparation of the feedstock, but also other technologies such as cracking with gaseous or solid heat transport
media or in the presence of catalysts. The cracking reactors
discussed include not only the normal tube furnace but
also alternatives such as molten bath, entrained bed or
fluidized bed reactors; the economic aspects of the technologies are also discussed. Furthermore, the economic
questions concerning olefin production are discussed both
retrospectively and with an eye to the future.
Descriptions of material problems in tube furnace construction, process monitoring and quench coolers for the
recovery of heat from the furnace effluent gases complete
a book primarily intended for engineers and chemists concerned with the building and operation of pyrolysis plants.
Bibliographies for every chapter permit more intensive
study. When American units are quoted, they are usually
accompanied by their SI equivalents. In spite of the fact
that the book is focussed on the question of producing low
molecular weight olefins, it is also useful for understanding other thermal processes.
R . Rammler [NB 628 IE]
Lurgi GmbH
Frankfurt am Main (FRG)
743
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