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Book Review Electrophilic Aromatic Substitution. By R. Taylor

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BOOK REVIEWS
Electrophilic Aromatic Substitution. By R. Taylor. Wiley,
Chichester 1990. xvi, 513 pp., hardcover E 85.00. -ISBN
0-471-92482-2
Twenty-five years ago this same author (in collaboration
with R. 0. C. Norman) wrote the highly regarded monograph “Electrophilic Substitution in Benzenoid Compounds”. The present state of knowledge on electrophilic
substitution in arenes has now been systematically and comprehensively covered in an almost completely rewritten book
of eleven chapters. Heteroarenes are not included here, but
benzenoid compounds such as annulenes, metallocenes and
carboranes are. (Electrophilic substitutions in heteroarenes
are soon to be treated by this author in collaboration with
A . R. Katritzky in Volume 47 of the series Advances in Heterocyclic Chemistry.)
Electrophilic substitutions in arenes are among the classical reactions of organic chemistry that students have always
been introduced to early in their courses. The book’s preface
tells us that about one third of world chemical production
consists of arenes and substituted arenes. So, one might ask,
in a field that has been so widely studied and worked over,
is there much that is new to be reported? Indeed there is, as
this book proves.
The first two chapters (“Introduction” and “The Mechanism of Electrophilic Aromatic Substitution”) give a brief
but adequate account of the theoretical and mechanistic basis needed to understand the chapters that follow (the theory
of aromaticity; inductive, mesomeric and steric effects of
substituents; possible mechanisms of SEArreactions, such as
SE1,B-SE1,SE3,S,2 and A-SE2).Chapter 3 (“Hydrogen Exchange”) deals with the simplest types of electrophilic aromatic substitutions: deuteriodeprotonation (H/D exchange),
tritiodeprotonation (H/T exchange), protiodedeuteriation
(D/H exchange), protiodetritiation (T/H exchange) and deuteriodetritiation (T/D exchange) -all of which are reactions
of special interest from a mechanistic standpoint. Chapter 4
(“The Replacement of a Substituent by Hydrogen”) discusses fourteen reactions in which a substituent already present
in the arene ring undergoes electrophilic replacement by a
proton, ranging from protiodeauration through protiodealkylation to protiodesilylation. Also included in this
group of reactions from a mechanistic standpoint is the hydrolysis of arylmagnesium halide Grignard reagents (protiodemagnesiation). Chapter 5 (“Metallation”) deals with the
replacement of hydrogen atoms in arenes by metals (Li, Au,
Hg, B, TI, Si, Pb, Sb, Te, Rh, Pd); however, the only one of
these that has so far been categorized unequivocally as an
Angew. Chem. Int. Ed. Engl. 30 (1991) No. 3
0 VCH
electrophilic aromatic substitution is mercuration. Nevertheless, the author describes all the known arene metallation
reactions, and invites further experimental investigations to
remedy this gap in mechanistic knowledge. In Chapters 6 to
9 we find descriptions of electrophilic aromatic substitution
reactions that are more familiar to the average chemist, with
the various electrophiles arranged according to the periodic
system. Thus Chapter 6 describes reactions using carbon
electrophiles (e.g. Friedel-Crafts alkylations and acylations),
Chapter 7 describes reactions using nitrogen electrophiles
(e.g. azo couplings and nitrations), Chapter 8 deals with reactions involving oxygen, sulfur and selenium electrophiles
(e.g. sulfonations), and Chapter 9 covers electrophilic halogenations. Chapter 10 (“The Replacement of a Substituent
X by a Substituent Y”) deals with 63 known ipso-substitution reactions, ranging from silyldelithiation through sulfodealkylation to halogen exchange. Lastly, in Chapter 11
(“Quantitative Evaluation of Electronic and Steric Effects in
Electrophilic Aromatic Substitution”) we learn something
about quantitative relationships between structure and reactivity in electrophilic substitutions of arenes, about suitably
modified Hammett equations with detailed tables of substituent constants and reaction constants, and about the factors
that determine the ortholpara ratio in the product. A subject
index completes this comprehensive work; however, there is
no index of authors.
There is scarcely any aspect of electrophilic substitution of
arenes that is not covered in this book, as can be judged from
the inclusion of about 2700 literature references and 127
tables. The clear and attractive typography and lucid formula schemes make the book easy to read, and one quickly
becomes absorbed. In doing so one comes across unexpected
recent results, even concerning named reactions that have
long been familiar. Anyone who seeks comprehensive and
reliable information about electrophilic substitution in arenes would be well advised to borrow this book from the
nearest library, which certainly ought to have it in its collection. However, the comparatively high price means that not
many readers are likely to have their own copy for reference.
Christian Reichardt [NB 1093 IE]
Fachbereich Chemie
der Universitat Marburg (FRG)
The Chemistry of Metal Cluster Complexes. Edited by D . E
Shriver, H . D. Kaesz and R. D. Adams. VCH Verlagsgesellschaft, Weinheim 1990. 439 pp., hardcover
DM 164.00.-ISBN 3-527-28047-2
Not surprisingly for such a rapidly expanding field of research, another monograph on the chemistry of metal clusters has now appeared; it is certainly the most up-to-date and
well presented. This is not least because of the publishers’
attractive production of the book. Like its predecessors
(B. F. G . Johnson (Ed.): Transition Metal Clusters, Wiley,
Chichester 1980; M. Moskovits (Ed.): Metal Clusters,
Wiley, New York 1986; B. C. Gates, L. Guczi, H. Knozinger
(Eds.): Metal Clusters in Catalysis, Elsevier, Amsterdam
1986) this monograph edited by acknowledged experts is a
collection of individual contributions by well-known authors, some of whom have published similar articles elsewhere. This naturally means that the book does not have the
character of a unified whole. Despite the evident efforts by
the editors to achieve some unity, it remains true that the
chapters of this book are independent articles; in this situa-
Verlagsgesellschafr mbH, W-6940 Weinheim, 1991
+
0570-0833/9lj0303-0337 $3.50 ,2510
337
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