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Book Review Conformational Analysis. By E. L. Eliel N. L. Allinger S. J. Angyal and G. A

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In Chapter 1, a n introduction on the nature of light is
followed by a discussion of the measurement of light, the
characteristics of various light sources, and the production
of monochromatic light. This is followed, in Chapter 2, by
a description of primary photophysical processes, starting
with energy level diagrams and electronic states, then
fluorescence and energy transport, and finally reactions in
gases and in solution. The chapter ends with a discussion of
the photographic process and examples of photochroism
and photoisomeric reactions. Chapter 3 deals with chemiluminescence in gases and liquids, and Chapter 4 with
luminescence in biological systems. After a description
of biological structures, Chapter 5 discusses photosynthesis.
This is followed by descriptions of the phenomenon of
vision, photoperiodism, phototaxis, and the action of UV
light on biological cells.
The book ends with seven appendices containing a number
of data and descriptions of instruments including the laser.
In view of the range of material covered, the choice of
examples is necessarily limited However, the selection of
subject matter is often not very suitable. For example, it is
superfluous t o describe photographic processes and their sensitization or lasers in this context, when protolytic reactions,
redox processes, and Rash photolysis are not dealt with. On
the other hana, a preparatory treatment of the problems of
energy transport is presented in the first part although this
phenomenon in photosynthesis is not even mentioned in the
second part. A better correlation of the physical and biological parts is to be hoped for in the second edition.
The treatment of biological structures deals with ideas that
were current in 1959, but not with the more recent results.
The chapter o n photosynthesis is too brief, and inaccurate in
places. On p. 86, the energies of the emission bands are given
H. T. Witt
[NB 551 IE]
incorrectly.
Ligand Substitution Processes. By C. H. Langford and H. B.
Gray. From the series “Frontiers in Chemistry”. W. A.
Benjamin, Inc., New York-Amsterdam 1965. 1st Edit.,
viii, 111 pp., numerous figures, $9.35.
At a time of rapid progress in the study of ligand exchange
processes the appearance of this monograph, presenting a
modem interpretation of “classical” results, is to be welcomed.
An introductory chapter lays down a new principle for the
classification of ligand exchange reactions in which both the
mechanism established from kinetic studies and the molecular processes involved are taken into consideration. The
applicability of this classification, 4s auplied to the most
thoroughly studied complexes of P;(irl and of CO(III),is
demonstrated in the two following chapters. More recent
investigations o n other metals are also briefly mentioned,
but the methods of investigation are n o t discussed. Each
chapter ends with a summary and a list of original publications (up to 1965)
In view of the small size of the book, some knowledge of coordination chemistry and reaction kinetics is presupposed by
the authors. Nevertheless, the book is very clearly written
and excellently illustrated, and can be recommended even as
a n introduction to this special field.
2%. Kruck
[NB 569 IE]
Advanced Physical Chemistry. Molecules, Structure and
Spectra, by J . C . Davis j r . The Ronald Press Conipanv,
New York 1965. 1st Edit., x, 632 pp., numerous figures,
cloth $ 12.00.
Physical chemistry is not only an independent scientific
discipline, but also serves as a link between physics and
chemistry. One of the tasks of a textbook of physical chemistry is therefore to introduce the chemist to the physical
methods that are important to him, including those o f
theoretical physics. A few decades ago, thermodynamics was
undisputedly the most important field of theoretical physics
382
as far as chemists were concerned; nowadays, however, a
knowledge of molecular dynamics, quantum theory, statistical mechanics, and the theory of magnetism is becoming
increasingly important in chemical research. Accordingly,
at least half of the present textbook is it sort of “Theoretical
Physics for Chemists”. The adjective “advanced” in the title
means only that the subject matter goes beyond the usual
training in physical chemistry. No previous knowledge is
required, apart from some experimental physics and as much
mathematics as the average American reader might be
expected to possess.
The principles of classical mechanics and of quantum
mechanics are introduced in a rigorous form and are clearly
interpreted. The leader should be able to gain an understanding of operator calculus from this textbook. One chapter is
devoted to the fundamentals of statistical mechanics and its
relation to thermodynamics. Further chapters deal with the
theory of angular momentum, spin, and magnetic moments,
the approximatiorr methods of quantum mechanics, and the
theory of the absorption and emission of light. Special
attention is given to .molecular rotation (also with respect to
applications of microwave spectroscopy), the theory of
molecular vibrations (but stopping before normal coordinate
analysis), and the fundamentals of nuclear magnetic resonance spectroscopy. The treatment of the relationship
between electronic structure and UV spectra is somewhat
short, and the theory of chemical bonding us really only
touched upon.
The book is well compiled from the didactic standpoint,
logically arranged, and as lucid as possible in its reasoning.
The main emphasis is always placed on the fundamental
relationships. Special applications are presented for illustration rather than as ends in themselves. A wealth of interesting
exercises (unfortdrately the mlutions are not given) enables
the reader t o check haw much he has understood.
In many places the reader may notice a lack of absolute
rigor or failure to mention details that are not unimportant.
The transitian from the Lagrange function to the Hamiltonian
function should (like the transitian from internal energy to
enthalpy in ttermodynamics) be substantiated. An important
point in the derivation of the Planck radiation formula is
that Bose statistics for light quanta are used. The derivation
given for the Boltzmann velocity distribution is not quite
rigorous. In Chapter 7, the term “hydrogen-like functions”
is used in a very unconventional sense. The Dirac 6 function
is incorrectly defined on p. 504. The statement (p. 454) that
VB functions are known as bond orbitals is also incorrect.
On the other hand, one finds many critical comments on the
concepts introduced. The author generally avoids oversimplified “proofs”.
Anyone concerned with or interested in molecular spectroscopy or questions of molecular structure in general will
find what theoretical principles he requires in this book.
W. Kurzelnigg
[NB 561 IE]
Conformational Analysis. By E. L. Eliel, N . L. Allinger, S. J .
Angyal, and G. A . Morrison. John Wiley & Sons,Inrz,
New York-London 1965. 2nd ed., xiii, 524 pp., numerous
illustrations, paper $ 15.00.
The object of stereochemistry is to correlate the spatial
arrangement of the atoms in molecules with the physical and
chemical properties of the latter. This undertaking formerly
met with only limited success, since the internal mobility of
the molecules, which seemed excessively complicated, was
disregarded. I t is now accepted that it is unnecessary to
consider all steric arrangements (e.g. conformations) of
mobile molecules. Many “pure” substances simply consist of
a few molecular species (mostly conformers), which (at
present) cannot be separated owing to their rapid interconversion.
Conformational analysis consists in the determination of the
composition of these mixtures by physical methods, and so
Angew. Cham. internat. Edit. 1 V d . 6 (1967) / No. 4
permits the correlation of the steric arrangement of the
component molecules with their physical properties (e.g.
energy). The intramolecular strains deduced from these
properties are then used for the analysis of specifically arranged transition states, so that a direct relationship is found
between molecular structure and chemical properties.
This work testifies to the fruitfulness and the wide applicability of this young discipline of organic chemistry.
The book deals with theoretical aspects of thermodynamics,
kinetics, ultraviolet, infrared, microwave, and N M R spectroscopy, rotatory dispersion, and molecular refraction. It
contains tables of rates, strain energies, equilibria, and
rotation barriers. The different interests of the authors ensure
a many-sided balance of subject matter, as is shown by the
following randomly-chosen key phrases: conformational
energy, kinetic determination of equilibria, isomerization of
hydrocarbons (with methods), 2-, 3-, a n 4-alkyl ketone
effect, gem-dimethyl effect, 1,Z-diaxial rearrangement, synaxial interaction, medium and large rings, refiex effects, synthesis of cortisone from cholic acid, A2-effect, anomeric
effect in pyranosides, deformation of the cyclohexane chair,
flexible form, entropy in equilibria, specific reactions of
sugars, terpenoids, and steroids. The authors offer interesting
rationalizations of a number of “rules”, such as the von
Auwers rule, the octant rule, the Brewster rule, and the
phenylosotriazole rule.
A very large part of the book is concerned with the chemistry
of cyclohexane and its derivatives, in which conformational
analysis first took root, and in which it still finds its most
successful applications. The reason for this is the small
number of conformers involved and the depths of their
energy minima.
It is regrettable that the designation of partial conformations
by “syn-clinal (sc)”, “anti-periplanar (ap)” etc. was not used
consistently by the authors, since this together with the
sequence rule (which is not mentioned) permits a simple and
comprehensive description of any conformation.
Unfortunately, the four reactions given on pages 28-30 d o
not illustrate the Curtin-Hammett principle in a convincing
manner. The first example is open to another interpretation
(see footnotes on pp. 29 and 30), while the other three are
really different cases of “steric” control of a reaction in which
two “stereoelectronic” routes are possible. The 2: 1 excess of
the erythru product described on p. 34 scarcely can have
resulted from the reaction of methylmagnesium bromide
with 3-phenyl-2-butanone.
In spite of a few such minor shortcomings, the book by these
four authors from the U.S.A., Australia, and England is an
outstanding contribution t o stereochemistry. The book is
really absorbing in many places, and should not be missed by
any diligent student or research worker. It gives a review,
both panoramic and detailed, of the field of conformational
analysis. The book also shows that the originally qualitative,
and hence simple method has now entered a much complicated, but quantitative phase.
[NB 514 IE]
A . S. Dreiding
Regisfered names, frademarks, ctc. used in this journal, even without specific indicafion thereof, are not be considered unprotected b y law.
1967 by Verlag Chemie, GmbH.
- Printed in Germany by Druckerei Winter,
Heidelberg.
411 rights reserved. No part of this journal may be reproduced in any form whatsoever, e.g. by photoprint, microfilm, or any other means, without
written permission from the publishers.
Editorial office: Ziegelhauser Landstrasse 35, 6900 Heidelberg, Germany, Telephone 24975. Telex 46 1855 kemia d, Cable address: Chemieredaktion
Heidelberg.
.
Editor: H . Grunewald Translation Editors: A . J . Racksrraw and A . Stimsan.
Publishers: Verlag Chemie GmbH. (President Eduard Kreuzhage), Pappelallee 3, 6940 Weinheim/Bergstr., Germany, and Academic Press Inc.
(President Walter J . Johnson), 1 1 1 Fifth Avenue, New York 3, N.Y., USA, and Berkeley Square House, Berkeley Square, London, W. 1. England.
Coirespondence concerning advertlsements should be addressed to Verlag Chemie, GmbH. (Advertising Manager W . Thiel). Pappelallee 3.
6940 Weinheim/Bergstr.. Telephone Weinheim 3635, Telex 4655 16 vchwh.. Cable address Chemieverlag Weinheimbergstr.
Atigew. Chem. infernat. Edit.
Vol. 6 (1967) / No. 4
3 83
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