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Book Review Georg de Hevesy. 1885Ц1966. Festschrift. Edited by G. Marx

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In the book’s 14 chapters the different subdivisions of the
topic are described by 15 expert authors, who have themselves made important contributions to research i n these
fields. The latest developments in high pressure apparatus
are not reported, however. Following an introduction written by the editor (Chapter 1 , 18 pp.). which briefly outlines
the main physical-chemical principles underlying the effects
of pressure on reactions in compressed solutions, 0. E-ynerin
Chapter 2 (31 pp.) introduces empirical group increments
for calculating molar volumes of many types of aliphatic,
carbocyclic and heterocyclic compounds; these are as simple
to use as the Benson increments for calculating enthalpies of
formation. With the help of these molar volumes it is a simple matter to estimate the reaction volumes which are important for assessing pressure effects.
Chapters 3 (50 pp., S. D.Haman) and 4 (23 pp.. M . Sasaki
and J. Osugi) are concerned with pressure effects on chemical
equilibria (e.g. for conformers, cis-trans double bond isomers, ionization reactions, etc.), and with kinetic isotope
effects, especially the pressure dependence of the tunnel
effect in hydrogen transfer reactions. Here the experimental
results are compared with model calculations where these are
available. In Chapter 5 (20 pp.) 7:Asano discusses the effects
of pressure on the hindered rotation in aniides and on the
cis-trans isomerization of compounds containing N = N,
C = N and C = C bonds. The use of dynamic NM R spectroscopy at high pressures as a method for such studies is described. I n Chapter 6 (61 pp.), which is devoted to pericyclic
reactions, G. Jenner includes a detailed discussion of DielsAlder reactions, whose pressure dependence has been studied very thoroughly. Also discussed here are other cycloaddition reactions ([2 21-, [6 41-, [8 21- and 1.3-dipolar
cycloadditions), en-reactions, and sigmatropic and electrocyclic rearrangements. Emphasis is placed here on the types
of information which activation volumes and reaction volumes contain in relation to reaction mechanisms.
Chapters 7 (34 pp., K . R. Brower), 8 (16 pp., E. Whalley
and W J. LeNoble) and 9 (29pp.. I.: M . Zhulin) deal with
pressure effects on anionic, carbocationic and free radical
reactions, respectively. Topics discussed in these chapters
include acid-base equilibria, hydride transfer, nucleophilic
substitutions, additions and eliminations, the problem of the
classical versus the non-classical norbornyl cation, polymerization reactions, and the decomposition of azo and per-ester
compounds. Here again mechanistic problems are in the
foreground. In the following two chapters the main emphasis is on preparative organic chemistry. Chapter 10 (20 pp.,
A . Rahm) describes, amongst other reactions, the additions
of organosilicon and organotin compounds to C = C and
C = 0 bonds at high pressures, which are of particular interest for synthetic purposes. Under the title “Synthesis” in
Chapter 11 (53 pp.), J. Jurczak provides an impressive review of reactions of importance in preparative chemistry
which only proceed with good or very good yields at high
pressures. This chapter is rounded off with examples of natural products syntheses in which the key steps require high
pressures.
Chapter 12 (23 pp., R. Schmidt and H.-D. Brauer) and 13
(46 pp., K. Heremans) describe respectively the pressure dependence of photophysical and photochemical processes
(such as intersystem crossing and the deactivation of excited
states), and aspects of bioorganic chemistry, e.g. the effects
of pressure on the structures of proteins and on enzyme
activity. In the final contribution (Chapter 14, 12 pp.) W J.
LeNoble discusses the sorts of conclusions regarding mechanisms that can be drawn from pressure effects, taking a number of carbene and fragmentation reactions as examples.
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1536
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Since this monograph has been written by a large number
of authors representing very different chemical specialisms,
which range from physical chemistry to preparative organic
chemistry, it should appeal to readers with widely varying
interests, and is a mine of information on published work
which is scattered throughout the organic and physical
chemistry journals, and is therefore difficult to keep track of.
The literature citations extend up to 1986 inclusive. The coordination achieved by the editor is commendable. This has
undoubtedly succeeded in avoiding over-frequent repetition
of the same phenomena in different chapters. However, there
are a few instances where it is pleasing to find the same
experiment discussed from different points of view. There
remains now the question as to what readership this book in
the series “Studies in Organic Chemistry” is aimed at. Foremost undoubtedly is the research chemist who already has a
basic knowledge of high pressure chemistry, and may need to
carry out his o r her own high pressure experiments.
It is difficult to understand why the price is so high. The
authors’ typescripts have been directly reproduced, and with
modern text processing methods there can be no objection to
this. However. one would expect the considerable reduction
in production costs achieved by this means to keep down the
purchase price. The Fact that the price is much too high,
unjustifiably so in my opinion, is unfortunately likely to
prevent this monograph. which is full of useful information
for non-specialists also, from reaching a wider readership.
Frank-Gerrit Klurner [NB 982 IE]
Fakultiit fur Chemie
der Universitlt Bochum (FRG)
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A> VCH Y~rlu~.~~c?Srlls~huJt
mhH, 0-6940 Weinheim.I989
Georg de Hevesy. 1885-1966. Festschrift. Edited by G.
Marx. Akademiai Kiado, Budapest 1988. 165 pp.. hard
cover. DM 34.00. -ISBN 963-05-5230-2
This book contains the typewritten texts of the papers
presented at a meeting held at the Eotvos University in Budapest on 26September 1985 to commemorate the hundredth anniversary of the birth of Georg von Hevesy. First
Gycirgy Marx gives, by way of an introduction, an outline of
Hevesy’s life and work. After studying in Budapest and at
German universities he undertook a period of research with
Rutherford in Manchester from 191 1 to 1914. This familiarized him with radioactivity, and was also the start of a
lifelong friendship with Niels Bohr. His teaching and research activities at Budapest University were interrupted by
World War 1, and shortly after the end of the war they came
to a stop due to the revolution. Hevesji emigrated to Denmark for the first time. From there he went in 1926 to
Freiburg as Professor of Physical Chemistry. In 1934 he
moved for the second time to Denmark. In 1943 he fled to
Stockholm, and in 1945 became a Swedish citizen. His life
ended in 1966 in Freiburg--perhaps finally reconciled? His
relationship with Hungary is discussed at the end of this little
book by Gubor Pa116.
Hevesy’s scientific work was extremely varied, as becomes
clear from Marx’s article, and the quantity of it was also
quite large, as is evident from the bibliography compiled by
Hilde Levi, which lists 397 publications. In 1913, together
with Friedrich Paneth, he invented radioactive labeling, and
soon began to apply it to problems for which this was the
only available method, such as self-diffusion in metals. The
discovery of element 72, hafnium. using X-ray fluorescence
spectroscopy, belongs to his first Copenhagen period. His
time in Freiburg was dominated by geochemical topics such
OS70-0833/NY/I I f 1-1536 $02.SOiO
A n p w . C h m . I n ! . Ed. EngI. 28 (1989) N o . I I
as the dating of geological specimens using the radioactive
decay of lead isotopes. Back once more in Copenhagen, he
invented neutron activation analysis with Hilde Levi, then
became increasingly involved in the applications of artificial
radioactive isotopes in biology and medicine, initially using
32P; from this work nuclear medicine developed. For his
research on isotopes as tracers for investigating chemical
reactions he received the Nobel Prize for Chemistry in 1943.
The lectures were linked under the general heading “Interdisciplinary Applications of Nuclear Methods”. Only the
first of these relates directly to Heves.~;in this Gustrlf‘Arrhenius and Hilde Levi give a review of his geochemical and
cosmochemical period from 1922 to 1935 (26 pp.). Rudolf
MijJkiuer describes the beginnings of the precision gammaray spectroscopy technique which is named after him
( I 3 pp.). and following this Vitulii Goldanskii then discusses
the method in greater detail. using examples of applications,
mainly in the field of biomacromolecules (35 pp.). Next
comes a contribution by Ferenc M t w i on the neutron spinecho technique, again applied mainly to biomolecules; here
an important field of research which originated at the place
of the meeting was described (1 1 pp.). The book ends with a
detailed review by Kai Sieghahn of the development and still
continuing refinement of the ESCA (electron spectroscopy
for chemical analysis) method (37 pp.).
This little book will be mainly useful to readers who are
engaged in work in the fields dealt with in the individual
papers. It should also be in every department library, as a
way of keeping alive the memory of Grorg von Hevesy, a
gentleman scientist who had the resources to enable him to
work for a considerable time without a salary, and thus to
remain literally his own boss. There is something in the view
which is occasionally put forward that the decline of science
in this country began with the disappearance of the wealthy
“Privatdozenten”, for these people were truly independent.
Ciinter Herrmann [NB 990 IE]
Institut fur Kernchemie
der Universitgt Mainz (FRG)
Carbocycle Construction in Terpene Synthesis. By Tse-Lok
Ho. VCH Verlagsgesellschaft, Weinheim/VCH Publishers,
New York 1988. xiv, 768pp.. hard cover, D M
260.00. - ISBN 3-527-26582-1 10-89573-279-3
This book by Ho o n ring-forming reactions in terpene
synthesis is a long one. It has 760 pages, 1600 references and
about 7000 structural formulas which are correctly drawn in
nearly every case. What does the book offer the reader that
is new? No places the ring-forming reaction as the central
step in every synthesis, with the synthesis proceeding around
it, before it and following it. This viewpoint strikes the reviewer as misleading, or at least biased. It can sometimes be
appropriate, as in some of the more spectacular cationic
cyclizations, e.g. in the synthesis of alnusenone (page 290),
but it is an overstatement in many cases, especially for syntheses of which ring formation is a comparatively insignificant part, e.g. the formation of the second cyclopentane ring
in the synthesis of pentalenolactone (page 92). This overemphasis on ring formation is reminiscent of total syntheses of
natural products in which, say, 15 laborious stages are needed to prepare the precursor for the ingenious one-stage ringclosing reaction.
The book treats the subject defined above in 11 chapters:
Robinson annelations, aldol condensations, Michael aldol
condensations, Claisen and Dieckmann reactions, in-
tramolecular alkylations, cationic cyclizations, Diels-Alder
reactions, other thermal processes (i.e. [3 + 21-, [4 31-additions, etc., Wittig and Claisen rearrangements, electrocyclizations, etc.), free radical cyclizations, small ring syntheses
(Simmons-Smith reaction, carbene chemistry, photochemical formation of cyclobutane, etc.), ring enlarging and ring
contraction reactions. and a chapter on “transitory” ring
formation reactions, i.e. those that subsequently serve other
purposes, e.g. cyclopropane + gem-dimethyl.
The book also takes into account the most recent published work. Even the main text contains quite a number of
1987 references. while the 50 or so references contained in the
appendix are mainly to papers published in 1988.
Unfortunately the information content of the reaction
schemes is very scanty. Only for the centrally placed ringforming reaction are some details of the reactants rather
casually included, and even here without giving yields. More
information here would have been very useful for quick reference, and rapid access to information is without doubt one
of the main purposes of such a book.
The content of the book overlaps to a large extent with the
chapters on mono-, sesqui- and triterpenes in the series “The
Total Synthesis of Natural Products” by ApSimon. While
it is true that H o is seven to eight years more up-to-date.
ApSirnon is better in information content and clarity.
Finally, a few errors will be mentioned, more in order to
show that the reviewer has read the hook carefully than by
way of serious criticism. On page 481 a CH, group is missing
from the route to nootkatone, on page 335 E/Z-ocimenone
was converted using isoprene, not ocimene, and the relevant
reference is Adams (1975), not Ayar (1973. 1975). On page
215 the CH, and ClCH, groups are shown in the wrong
positions in the ishwarone synthesis. But, as has already been
said, these are unimportant details in a work such as this.
To summarize, the book constitutes a new attempt at presenting the formidable variety of terpene syntheses according to a different method of classification based on their
ring-forming reactions. Since every such new approach offers the possibility that in thumbing through the book one
can learn something new, or see something which is already
familiar from a different viewpoint, it is a useful book for the
synthetic chemist and, although rather expensive, is worth
buying.
Georg Frater [NB 966 IE]
Givaudan Forschungsgesellschaft AG
Dubendorf (Switzerland)
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Analytical Artifacts: GC, MS, HPLC, TLC and PC. (Journal
of Chromatography Library, Vol. 44). Edited by B. S.
Middlediitclz. Elsevier, Amsterdam 1989. 1033 pp., hard
cover, HFI 495.00. -ISBN 0-444-871 58-6
Every honest analyst has at some time detected in his
samples substances whose presence has a t first seemed astonishing. In many cases it turns out, after further careful investigation, that these have found their way into the analytical
samples in mysterious ways, through the operation of
“Murphy’s Law”, during some purification or sample preparation step, or even during sampling. In publications mention of such occurrences is either shyly omitted, since no one
willingly admits to having been stupid, or hidden away in
incidental minor comments. After all, why not let others
make the same mistakes?
It is surprising, therefore, that despite this there are so
many wrong chromatographic interpretations to he found in
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