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Book Review Phase Transfer Catalysis. Principles and Techniques. By C. M. Starks and C. Liotta

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BOOK R E V I E W S
Phase Transfer Catalysis in Organic Chemistry. By W. P.
Weber and G. W . Gokel. Springer Verlag, Berlin-Heidelberg-New York 1977.280 pp., bound, DM 64.70.-Phase
Transfer Catalysis. Principles and Techniques. By C. M .
Starks and C. Liotta. Academic Press, New York-San
Francisco-London 1978. 365 pp., bound, $ 38.00.
Phase transfer catalysis is a term characterizing an essential advance in chemical synthesis techniques over the last
decade. Several review articles have already appeared”’, and
now we have the first two monographs (there is already a
publisher’s announcement of a third‘”’). They are written by
authors who have taken active part in the development of the
technique, Starks even coining the term “phase transfer catalysis”. The books have been conceived and printed in a
pleasantly readable manner, and the number of printing errors has been kept within limits. Both books have been
slightly inflated by the repetition of the same subject matter
in several chapters and by the tabulation of every compound
treated. together with yields, which seems unnecessary in the
case of homologous or analogous series with little difference
between the individual members. In each book the material
in the synthesis section is arranged by the type of reaction:
simple substitutions, alkylations and condensations, methods
for carbene production, ylide reactions, oxidations and reductions, miscellaneous further phase transfer catalysis reactions ((hi\ i h the arrangement in Starks and Liotta). Efforts
have been made to cover the literature as comprehensively as
possible. Weber and Gokel cover it to the end of 1976, and
there is an appendix with further references from 1976-77,
arranged by chapter, giving a total of 650 references. Starks
and Liotta cover just 700 of the 900 references known to
them to the end of 1977. The field is developing rapidly; for
the period 1978-79, the present reviewer already has more
than 200 new references in his file!
There are marked differences in the way that the two
books deal with the theoretical foundations (Starks and Liotta take three chapters with 90 pages, Weber and Gokel one
chapter with 17 pages), and in their printing of typical preparative details (lacking in the case of Weber and Gokel).While
Weber and Gokel deal briefly with general, mechanistic, and
theoreticalproblems, StarksandLiotrahaveputalotofeffortinto
collecting data on the extraction of anions and cations into organic solvents, on the reactive behavior in different media, and on other fundamental questions. Kinetics,
limiting conditions, and possible mechanistic alternatives are
discussed, and hints are given on the choice of the catalyst
and the solvent and also of the conditions for a new reaction.
Weber and Gokel d o give all this material as well, but in a
very summary form. Although we are still far from being
able to predict the catalyst activity or the exact course of a
new phase transfer catalysis process, Starks and Liotta give
the essential starting points for a general theory, and in the
case of substitution reactions a fair amount of progress has
been made. Difficulties arise in the explanation of alkylation
and carbene production in the presence of concentrated
caustic soda. Starks and Liotta’s critical approach, which is
otherwise impeccable, breaks down here, for example, in the
use of different values for the selective extraction of OH (p.
173: B r - is 10’ times more readily extracted than O H - , in
Table 7, p. 24, however, i t is only 1650 times. Although in
~
[‘I
For example Angew. Chem. 86, I87 (1964). XY. 521 (1977): Angew. Chem.
Int. Ed. Engl. 13. 170 (1974). 16. 493 (1977).
[**I Phase Transfer Catalysis. By E. V. and S. S. Dehmlun,. Verlag Chemie International. N e w York and Weinhelm. in press.
Angrn, Chow. Int. Ed. EnKI. I H llY7YI Nu. 7
other places the difficulty of dissolving tetrabutylammonium
hydroxide in benzene is mentioned, the extraction value given in Table 3 on p. 18 is obviously wrong). Notwithstanding
these minor blemishes, this is a very good book. Despite the
better layout and better paper in Weber and Gokel, Starks
and Liotta’s book must still be the first choice for anyone
who cannot wait for further developments.
Ekkehard V . Dehrnlow [NB 471 IE]
Principles of Chemical Kinetics. By G. G. Hammes. Academic
Press, New York 1978, x, 268 pp., bound, $ 19.50.
Despite some pleasing recent publications, there is still a
lack of introductory books on reaction kinetics that deal
with the fundamentals of formal kinetics and at the same
time lead on to the major areas of current research. The
present book partly fills this gap. Based on the book by
Amdur and Hammes, it has now been revised by Hammes
after Amdur’s death. It contains chapters on formal kinetics,
collision theory, and the theory of the transition state. After
examples of bimolecular and unimolecular gas reactions and
the more recent theories concerned with them, the author
discusses molecular beam experiments and experiments on
energy transfer (including recent work with lasers). Shock-wave
techniques are dealt with in an appendix. Next comes a survey
of reactions in solution. first on the basis of electrochemical
relationships and then oriented toward more recent techniques
such as relaxation methods and NMR spectroscopy. After
a survey of protolytic reactions and acid-base catalysis, the
book closes with a chapter on enzyme kinetics.
The author has succeeded in producing a lively and compact
presentation of selected topics in modem reaction kinetics.
Because it is only a selection, a number of areas have obviously
been touched on only lightly if at all. Because of its choice
of topics of current interest, the book can be highly recommended as an introduction to some major areas of modern
research in reaction kinetics, and as a supplement to the
basic lectures of a course on kinetics for advanced students.
Jiirgen Doe [NB 466 IE]
Inorganic Polymers. By N . H . Ray. Academic Press, London
1978. viii, 174 pp., f 8.40.
The book gives a concise account of the current stage
of development of inorganic polymers, which are defined here
as large molecules with no carbon in the main chain and
with mainly covalent bonds. Polyphosphoric acid esters, and
in particular silicones, which come under this definition, are
not dealt with because of their high proportion of organic
side groups. There is a brief discussion of the most important
physical parameters: modulus of elasticity, tensile strength,
brittleness, solubility, and glass transition temperature. From
the fact that most inorganic polymers, even if they are highly
cross-linked, can be heated beyond the glass transition temperature without decomposition (which is generally not true of
organicpolymers) and can be processed in this way, the author
deduces that the earlier assumption that linear inorganic
polymers could be produced by reducing the functionality
of elements like B, Si, or P is fundamentally false.
Inorganic polymers may be classified as follows on the
basis of the coordination number of the element(s) making
up the polymer skeleton:
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