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Book Review Chemical Reactions at High Pressures By K. E. Weale E. and F. N

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Direct irradiation of ( l b ) leads only t o (2h), whereas ( I c )
rearranges to give only (3c). These results support the view
of Brewer and Heaney that the cyclooctatetraenes are formed
vi u the excited singlet state and the semibullvalenes via the
excited triplet state. / J. Amer. chem. SOC.90, 4465 (1968)
[Rd 918 IE]
1,2-Diaryl-2-arylthiovinyl-2,4,6-trinitrobenzenesulfonate( /)
has been obtained by G . Capozzi, G . Melloni, G . Modenu, and
M . Piscitelli by addition of arylsulfenyl 2.4.6-trinitrobenzenesulfonates t o tolan and 4,4’-dimethyltolan. The arylsulfenyl
derivatives were prepared from arylsulfenyl chlorides with
silver 2,4,6-trinitrobenzenesulfonate,and were not isolated.
Examples of ( I ) : R = R1 = H, m.p. = 1O9-11O0C: R = H ,
R’ = p-Cl, m.p. 139-14OOC; R = R1 = CH3,
New transition metal complexes with the carbaphosphollide ion
(3)-1,7-BgHsCHP(CH3)- are described by L. J. Todd, I. C.
Purr/, J . L. Little, P . S . Welcker, and C. R . Peterson. When
1,7-BloHloCHP is heated in piperidine it forms the piperidinium salt of (3)-1,7-B9HloCHP-, the tetramethylammonium
salt of which reacts with N a H and then with FeC12 t o give the
red-violet anion [(3)-1.7-B9H&HP]2Fe2-. This anion can be
I )~ ) ] Z F ~
alkylated with CH31 t o give [ ( ~ ) - ~ , ~ - B ~ H ~ C H P ( C( H
(brown isomer, m.p. = 239.5-240.5’C;
red isomer, m.p.
233-234 “C). A cocrystallite containing both isomers forms
deep red orthorhombic prisms (a = 13.66, b = 13.96, c =
20.36 8, space group Pbca) o n sublimation. The unit cell
14.44, b ?= 13.79, c = 19.51 A.
of the brown form has CI
According t o the X-ray structural analysis of a cocrystallite
of ( I ) (formula shown without substituents), the C atom
in one of the polyhedra probably statistically occupies one
of the two positions marked in black. Similar complexes are
formed with Co*’ and Niz+. / J. Amer. chem. SOC.90, 4489
(1968) / -Kr.
[Rd 919 IE]
m.p. = 104-105 “C. ( I ) gives orange-red crystals, which can
be recrystallized e.g. from chloroformipentane and decompose in many inert solvents, particularly in the presence of
BF3, t o give the free sulfonic acid and a 2,3-diarylbenzo[blthiophene (2). Reaction with weak nucleophiles gives products such as (31,while strong nucleophiles form acetophenone
derivatives such as (41 as well as SO2 and trinitrophenyl
derivatives. The authors believe that 4 vinylcarbonium ion
(5) is formed as an intermediate in the decompositions. /
Tetrahedron Letters 1968, 4049 / -Kr.
[Rd 920 IE]
Chemical Reactions at High Pressures: By K. E. Weale, E. and
F. N. Spon Ltd., London 1967. 1st Edit., xiii, 350 pp..
numerous illustrations and tables, 70 s.
The chemistry of reactions at moderately high and very high
pressures has developed so vigorously in the last few years
that it is now hardly possible for one person t o write a really
comprehensive monograph covering the whole field. At the
same time, the meaning of the term “high pressure” becomes
more and more blurred. From this point of view it must be
recognized that, in spite of its comprehensive title, the present
monograph deals thoroughly with only a part of the field of
high-pressure chemistry - reactions in fluid phases at pressures up t o 15 kbar.
A short historical introduction is followed by chapters on the
influence of high pressures on the physical properties of
single-phase systems a n d o n the pressure dependence of
phase equilibria. This is followed by a survey of the experimental methods of high-pressure chemistry, including a few
sections o n the possible sources of danger of work at high
The main part of the book is made up of chapters on equilibria and reaction rates in liquids at high pressures. After a
rather theoretically oriented introduction to reaction kinetics
at high pressures, which establishes the concept of activation
volumes, many examples of the influence of high pressures on
organic reactions are given. Polymerizations are treated
particularly thoroughly. This chapter should be stimulating
even t o the specialist in the field.
Angew. Chem. infernnf.Edit. / Vol. 7 (1968) 1 No. I 0
Gas reactions at high pressures are also dealt with. The end
of the book comprises a 19-page section entitled “Reactions
at very high pressures” which deals with pressures above 15
kbar. In a later edition this section should either be omitted
entirely or so expanded that the fundamentals of the chemistry of the solid state at very high pressures are at least indicated. In the present form it merely presents a distorted
Weale cites about 1000 references to the literature, some as
recent as 1966. In the main chapters, o n the high-pressure
reactions of organic systems in particular, the recent literature has been considered extensively. The book will be of
greatest value t o those wishing to familiarize themselves with
the fluid state reactions at pressures up to 15 kbar, the basic
information on instrumental aspects, theoretical foundations
and experimental results. The book also provides a good
introduction to the original literature. I t will also be of
interest t o workers already concerned with high-pressure
K.-J. Range [NB 729 IE]
Aromatic Amine Oxides. By E. Ochiai. Elsevier Publishing
Company, Amsterdam-London-New York 1967. 1st ed.,
x, 456 pp.. 31 figures, 87 tables, bound Dfl 85.00/S8.15.0.
The author of this book started his studies o n the aromatic
amine oxides, which had been discovered in 1925 by J. Meisenheimer, as early as 1940. It was only many years later,
with the general growth of interest in the mechanism of
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