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Book Review Contemporary Heterocyclic Chemistry Syntheses Reactions and Applications. By G. R. Newkome and W. W

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BOOK R E V I E W S
Contemporary Heterocyclic Chemistry: Syntheses, Reactions and Applications. By G . R . Newkome and W. W .
Paudler. John Wiley - Sons, Chichester 1982. x, 422
pp., bound, L 30.80.
To present such a complex subject as heterocyclic chemistry in a 422 page monograph is not the simplest of tasks.
The authors’ aim is to cover heterocyclic chemistry with
particular emphasis on heteroarene chemistry.
The subject is divided into n-excessive and n-deficient
heteroarenes, according to the classical concept of Adrien
Albert, in order to allow its presentation as an entity. After
a (too brief) introduction to the nomenclature, a subject
which requires particular care because of the “arbitrary
growth” in several areas, the basic concept of this volume
is presented including MO calculations, dipole moment
and NMR studies (some tables showing electronic densities, dipole moments, ’H-, I3C-, and ”N-NMR data, pK,
values, UV data, bond lengths and MS fragmentation schemes of customary heterocycles are collected at the end of
the volume). The main part of the book consists of a discussion of the five-membered n-excessive and the sixmembered n-deficient heteroarenes, together with their
benzo-annelated analogues and derivatives, to which ten
and nine chapters, respectively, are devoted. Successful
classical methods and modern developments are always
dealt with side by side. A great deal of space is devoted to
the [2 + I]- and the [4+ 21-cycloadditions and to the additions of singlet oxygen to five-membered heteroarenes and
the subsequent reactions. Alongside pyridine, the six-membered heterocycles treated are the pyridazines, pyrimidines
(significantly under-represented in comparison to their importance), pyrazines, triazines, tetrazines and their benzo
derivatives.
Further chapters deal with SNand SEreactions as well as
radical reactions and photochemical transformations.
Among the nucleophilic reactions described in detail are
the EA (heteroaryne) and the ANRORC mechanisms. They
are followed by photoinduced valence isomerizations,
“ring scrambling” and [4+ 41-dimerizations of pyridines.
pyrazines and pyrimidines. Each class of compound has a
chapter on natural products and (a few) pharmaceutically
important compounds, devoted to it.
Heterocondensed heteroarenes are treated in a chapter
of their own. There then follows a comprehensive treatment of mesoionic heterocycles (sydnones, munchnones,
1,3-oxazolium-5-olates, 1,3-oxathioliumolates, 1,3-diazoliumolates and amides, 1,2,3,4-tetrazolium-5-thiolates) and
their manifold, synthetic potential. Particular attention is
paid to the three- and four-membered heterocycles; it is
noticeable that the photochemical C-C cleavage of epoxides to carbonyl ylides is not mentioned. Finally, two
chapters are concerned with some classical azepine, (benzo)diazepine and thiepin syntheses, together with methods
of producing some azocines and diheterocines; however,
the recently successful cycloaddition-ring enlargement
reactions are practically ignored.
References up to 1980 are included; the principal
sources quoted are monographs and review articles. Half
of the citations come from the last two decades. In spite of
this, one searches in vain for notions such as intramolecular
cycloadditions, frontier orbitals, or regio- and enantioselectivity. The literature citations are listed at the end of
each chapter which is irksome during intensive study. The
Angew. Chem. Int. Ed. Engl. 22 (1983) No. 9
formulas often look awkward because of the greatly varying bond lengths sometimes used. Better quality is to be
expected in a monograph of this price class.
Altogether this lucidly constructed monograph takes its
place between a text book and a progress report and guarantees, in an exemplary fashion, the chemistry student,
the chemist in research and in industry, as well as the
scientist of neighboring disciplines, an excellent and
speedy introduction to current chapters of modern heterocyclic chemistry by means of a clear conception and ample
literature citation. This book can be warmly recommended
to all in industry or university who are concerned with the
chemistry of heteroarenes.
Heinrich Wamhoff [NB 580 IE]
Institut fur Organische Chemie
und Biochemie der Universitat Bonn
Non-formal Kinetics. By R . Schmid and V. N . Sapunou.
Verlag Chemie, Weinheim 1982. xi, 199 pp., bound, DM
98.00.
The authors first introduce the reaction kinetic method
with the aid of simple examples. Elementary quantities,
such as the reaction rate constant or the half-life, are described in terms of the concentration-time curve, invariances I and I1 are also defined with the aid of linear transformations. Starting from these simplest cases and via parallel and series reactions, ever more complex, kinetic systems are treated. The kinetics of simple, catalyzed reactions are the starting point for the analysis of complicated,
catalyzed reaction paths, particularly with reference to biochemical applications.
In the second part of the book the authors introduce a
method of analysis of complex kinetics on the basis of the
kinetic techniques described, which proceeds largely without assumptions. Invariances I and 11, described at the beginning of the book, afford an opportunity to obtain preliminary information. The differentiated form of the ratetime curve plays a central role in the further analysis. A
procedure is described that allows a numerical expression
for the kinetic equations to be formulated by repeated correction of the rate-time diagram, even in the case of fractional orders of reaction and for catalyzed reactions. The
development of reaction mechanisms from the equations
so discribed is discussed.
Following the actual, kinetic analysis there is a chapter
concerning the influence of temperature on the rate constant. The Arrhenius equation and the Eyring equation are
compared and discussed in terms of the transition state
theory. Further chapters treat the influence of pressure, of
the solvent (with emphasis on empirical scales of polarity)
and of substituents. The appendix is concerned with free
enthalpy relationships and with the Exner analysis for the
determination of isokinetic relationships.
The book is useful both to the advanced student and to
the experienced practitioner, since it offers the one a summary of kinetic methods and the other a wealth of useful
details, which is systematized. The mathematical relationships in kinetic statements are clearly and distinctly formulated. The derivation of the Bodenstein principie might be
mentioned as an example. The effect of errors in measurement on the results of kinetic measurements is perhaps
treated too briefly; but it may be that this lies outside the
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