Journal of Molecular Structure, 29 (1975) 177-191 177

0 Ekevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

Book reviews

Organic Photochemistry, by J. M. Coxon and B. Halton, Cambridge University

Press, 1974, pp. vii + 196, price f4.20, paperback JL90.

The fascination of organic photochemistry and the current awareness of

the versatility and applications of photochemical methods are indicated by
the ever increasing number of papers published in this field.
This well-written addition to the Cambridge Chemistry Texts provides a
valuable and timely contribution to undergraduateand graduate courses on
the subject. A clear and concise introduction to primary photoexcitation
processes, the nature of excited states, and the modes of energy transfer,
leads to a succinct account of the main classes of organic photoreactions,
including geometrical isomerism, reactions of carbonyl compounds, di-n-
methane rearrangements, electrocyclic processes, sigmatropic rearrangements,
and cycloaddition reactions. In other texts, discussion of conservation of
orbital symmetry tends to be restricted to thermal concerted processes, with
an indication that the photochemical process will take place by the thermally
“forbidden” mode. In this book, concerted photochemical reactions are
discussed in some detail. Some photoreactions are formulated as concerted
which might well take place by a stepwise mechanism but give products with
the stereochemistry predicted by the Woodward-Hoffmann Rules for
Pericyclic Reactions because of steric or other considerations. In these
cases, the authors’ reservations on the concertedness of the reactions are
clearly indicated.
The interesting photoreactions of a-santonin are carefully and competently
explained and the mechanisms for the rearrangementsillustrated with studies
on simpler cyclohexadienone systems using Zimmerman’s approach. The
simpler method of Chapman, using a dipolar formulation for the excited
state, is not mentioned.
Photorearrangement reactions of cr,fl- and 0, r-carbonyl compounds are
exemplified and their mechanisms discussed. Photoxidation processes
involving triplet and singlet oxygen, photoreductions, photoinduced
nucleophilic substitution, and photogeneration of reactive intermediates
make up the fifth and final chapter.
The book provides a well balanced Survey of the salient points of interest
in organic photochemistry, illustrated with examples from recent literature
for which references are given. A six page comprehensive index is provided.

H. G. H.