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Book Review Grundzge der Radio- und Reaktorchemie (Fundamentals of Radiochemistry and Reactor Chemistry). By F. Hecht

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nuclear spin leads to the hyperfine structure of ESR spectra.
The chemical production of radicals and their measurement
in the ESR spectrometer are described only briefly, and the
main emphasis is laid on understanding the theoretical interpretation of spectra with hyperfine structure and of their
relation to concepts of the electronic structure of organic
radicals that can be derived from HMO theory and its refinements.
For this purpose the author confines his attention almost
wholly to radicals anions and cations of aromatic hydrocarbons and their aza derivatives, ions that have been
particularly thoroughly studied. The book thus gains much
in clarity and immediacy, especially as the author himself is a
recognized master of the field. Several of the inherent
problems are given a first, very clear interpretation without
making too great mathematical demands; examples are the
formation, by r-cr spin polarization, of a finite spin density
at the H atoms of benzene situated at the nodal plane of the
unpaired r-electron; the formation of negative spin densities
by z-li spin polarization; and the occurrence of relatively
large coupling constants on $-hydrogen atoms owing to
hyperconjugation.
A relatively short Appendix 1 follows, describing methods
of quantitative calculation used in estimating li-c and x-i:
spin polarization; here, however, considerable knowledge of
the techniques of quantum-mechanical calculation is assumed,
and this the ordinary chemist may often not possess.
In that section devoted to nitrogen-free and nitrogen-containing aromatic radical ions, it is shown how far predictions
from ESR spectroscopy can be extended, and to what extent
the results of quantum-mechanical calculations agree with
experimental results. The examples are excellently chosen to
demonstrate, by concrete cases, the extraordinary power of
prediction inherent in ESR spectroscopy.
The writing is concise and there is no unecessary repetition
The book requires concentrated reading, but it makes no
demand beyond the capacity of a student who is reasonably
familiar with HMO theory. This is an excellent book and it
is also an aesthetic pleasure owing to the splendid illustrations
of typical ESR spectra (most of them from the author’s
Zurich school), very clear schematic drawings, and the clean
and pleasant photomechanical reproduction of typescript.
References covering the literature up to the end of 1965 are
an aid to deeper study.
I t is to be hoped that the book has a wide circulation and
that the later volumes in the series will be equally successful.
K . Dimroth
[NB 809 IE]
Theorie der Molekiilspektren (Theory of Molecular Spectra).
By W. A . Bingel. From the series “Chemische Taschenbiicher”, Vol. 2, edited by W. Forst and H . Grunewald. Verlag Chemie GmbH, Weinheim/Bergstr. 1967. 1st Edit.,
206 pp.. 62 figures, 21 tables, bound D M 16.-.
This volume of the series “Chemische Taschenbucher” fills
a gap among German-language monographs o n molecular
spectroscopy, since apart from a few specialized works with
very narrowly limited subject matter,recent German literature
has nothing to offer as an introduction to the theory of
spectra. The author of the present book has therefore concentrated on the fundamental theoretical relations. A short
introduction is followed by a discussion of rotation and
rotation-vibration spectra; the vibrational and rotational
structure of electronic transitions is then also discussed.
Special attention is given to intensities and selection rules,
which are hardly mentioned in other, more experimentally
oriented books. The relation between the theory of the
chemical bond and UV spectroscopy is presented in a clear
manner. The author’s own special interests are reflected in a
very comprehensive discussion of the classification of the
electronic states of diatomic and triatomic molecules.
Since the book is intended primarily as a n introduction for
beginners, the treatment of infrared and Raman spectra has
396
had to be kept relatively brief. The author has tried to
explain the essential relations with the minimum use of formal
mathematics. The success of the treatment will depend on
the reader’s background knowledge. The book is well worth
the price, and it is to be hoped that it will be widely read,
particularly by the younger chemistry students.
Th. Ackermann
W B 792 IE]
Gruppentheorie fur Chemiker, Physiko-Chemiker, Mineralogen a b 5. Semester (Group Theory for Chemists, Physical Chemists, and Mineralogists in their 5th Semester and
Beyond). By K . Mathiak and P. Stingl. From the Series:
Hochschul-Studienbuch. Friedr. Vieweg und Sohn, Braunschweig, Akademische Verlagsgesellschaft, Frankfurt/M.
1968, paperback DM 9.80.
The modern chemist is making ever-increasing use of numerical methods (particularly quantum mechanical approximation methods) and sooner or later he is bound to have to
come to terms with the mathematical fundamentals of these
techniques. The present book by Mathiak and Stingl provides
an opportunity for him to get acquainted with the important
subject of group theory. Since the inclusion of numerous
examples and problems imparts the necessary “substance”
to the highly abstract subject matter, the reader can profit
considerably from a study of the sections entitled “Abstract
Group Theory”, “Symmetry Groups of Molecules”, and
“Representation Theory”. An additional section on “Vector
Spaces” has been included to furnish the necessary background. However, the section on the application of group
theory to Hiickel theory and molecular vibrations will do little
to stimulate the faith of the reader in this book, since it not
only contains many obscurities, inaccuracies, and mistakes,
but unfortunately also makes no mention of the most important applications of group theory: Selection rules and polarization of electronic transitions, band forms and polarization
for I R bands, degree of depolarization of Raman bands, as
well as considerations of the symmetry types of overtones
and combination frequencies in vibration spectra.
The apparently unavoidable mistakes in the character tables
are found in this book, e.g., in the groups C4. C4h. C6v. and
D4h.
K . Wilhelm [NB 787 IE]
Grundziige der Radio- und Reaktorchemie (Fundamentals of
Radiochemistry and Reactor Chemistry). By F. Hecht.
Akademische Verlagsgesellschaft, Frankfurt/M. 1958. 1st
Edit., x, 426 pp., 130 figures, 39 tables, paperback DM 25.-.
Though radiochemistry or nuclear chemistry forms part of
the curriculum of a number of universities where German is
spoken, there has until now been no satisfactory Germanlanguage textbook in this field, and the standard work for
radiochemists is therefore the excellent “Nuclear and Radiochemistry” (2nd Edit., 1966) by Friedlander, Kennedy, and
Miller. Because of its strong physical orientation, however,
this cannot really be recommended as an introduction. The
book by Hecht is intended to fill this gap, and can be said to
have succeeded in this object.
The book is divided into the following sections:
1. Nuclear-physical data, 2. Nuclear reactions, 3. Radiation
measurements, 4. Radiochemical procedures, 5. Artificial
radioactivity, 6. Nuclear reactors, 7. The effects of radiation
and radiation loading, 8. Use of radionuclides in industry
and medicine, and 9. Chemistry of hot atoms. The chapter
size ranges from 6 pages (Chapter 9) to more than 100
(Chapter 4). This very lucidly written book is of particular
value for students choosing radiochemistry as a subsidiary
subject as well as for practical chemists seeking a n introduction to experimental radiochemical techniques. However,
these are not the only readers to whom the extensive Chapters
3 and 4, which are outstanding for the expert knowledge
shown by the author, will appeal. Special mention should be
Angew. Chem. internat. Edit. J Vol. 8 (1969) 1 No. 5
made of the numerous figures and graphs. The various types
of reactors are discussed in Chapter 6, though the reviewer
would have expected a more detailed discussion of nuclearphysical principles (e.g. four-factor formula); however, this
is a shortcoming of all (even English-language) books on
radiochemistry and nuclear chemistry. Even physical principles are sometimes unfortunately not discussed at length;
there was no need to avoid mathematical formulations almost
completely. What the Friedlander-Kennedy-Miller book
lacks in chemistry, the Hecht book lacks in physics. One
would also have expected that in 1968 (the year of publication), the new position regarding the No isotope (dating
from 1963-1965) could have been presented; moreover, the
symbol Mv for element 101 (p. 241) was changed by the
IUPAC into Md almost ten years ago. These and other minor
points can, however, be corrected in a later edition.
The presentation and print are well below average, even if
allowance is made for the relatively low price. At least two
types of paper had been used in the reviewer’s copy, several
pages showed variation in print thickness or unsharp print,
and the paper binding delaminated after use for a short time,
so that the life of the book will probably be limited.
C . Keller
[NB 799 IE]
Synthesen mit Kohlenmonoxid (Syntheses with Carbon
Monoxide). By J. Fulbe. Vol. 10 in the Series “Organische
Chemie in Einzeldarstellungen”. Springer Verlag, Berlin,
Heidelberg, New York, 1967. 1st Edit., vii + 212 pp..
20 tables, D M 48.-.
Except for a few omissions, the author has succeeded in
writing a comprehensive monograph on syntheses involving
CO, and even experts in this field can find something new in
it. Hydroformylation, carbonylation. the Gattermann-Koch
synthesis, and carbonylation with Pd catalysts are described
in detail, irrespective of their technical importance. It is
obviously impossible in such a comprehensive book to
consider singly the entire literature quoted and to specify in
each case the importance of the individual works.
I t is mentioned in the Preface that, prior to their detailed
investigation, Reppe syntheses and Roelen reactions were
described after World War I1 in FIAT, BIOS, and CIOS
Reports. Despite this, workers engaged in the subsequent
intensive research in this field outside Germany hardly took
into account the previous investigations, with the result that
many aspects have been discovered twice. This could have
been brought to light still better by modifying the structure
of the book.
In connection with the reaction mechanisms, mention is
made again of the three-membered ring and ketene theory,
which was rejected years ago. On the other hand, only
footnotes are devoted to the important hypotheses proposed
a long time ago about the intermediates of hydroformylation
and carbonylation (FIAT, Houben-Weyl). At the same time,
a detailed account is found o n the mechanisms which were
proposed much later, and which closely resemble these
hypotheses.
This does not alter the fact that this is a very good book,
which can be recommended to those who work in this field.
H. Kroper
[NB 791 IE]
Comprehensive Biochemistry, Vol. 20: Metabolism of Cyclic
Compounds. By M. Florkin and E. H . Stofz. Elsevier
Publishing Co., Amsterdam, London, New York, 1968.
1st Edit., xiii + 533 pp., 135 figs., 34 tables; Dfl. 75.-.
This volume[l] deals with the biosynthesis and the degradation of complicated organic molecules arising in the metabolism of carbohydrates and amino acids. It bears witness to
111 Cf. Angew. Chem. 80, 974 (1968); Angew. Chem. internat.
Edit. 7, 901 (1968).
Angew. Chem. internat. Edit.
Vol. 8 (1969) No. 5
the great progress made in the last I S years in the elucidation
of structural relationships by new methods and improved
techniques. Not only is the literature well documented up to
1967, hut also a great number of quotations are included in
some cases. As a result, this book often makes it unnecessary
to consult the original articles for details. It also gives surveys
which enable the reader to familiarize himself with the
relevant material.
Discussing the isoprene derivatives, H . J . Nicholas describes
the synthesis, degradation, occurrence, and function of
vitamin A, a-tocopherols, vitamin K. ubiquinones, plastoquinone, carotinoids, squalene, and other terpenes, as well
as rubber. H e also discusses ecdysone and the giberellins,
together with their function and the regulation of the biosynthetic cycles between organelles. The metabolism of
steroid hormones and bile acids is discussed by D . B. Gorer,
whose account includes the formation and the conversion of
CIS, C19, and Cz1 sterols, the action of ACTH and other
hormones, the enzymatic hydroxylation and dehydrogenation
of the steroid skeleton, and processes of conjugation and
elimination. The author examines the reaction mechanisms
in great detail and also discusses the secondary conversion
of bile acids by intestinal microflora, though the products
of this conversion are only indirectly connected with biogenetic cycles.
The phenolic substances are divided into flavonoids (F. U‘P
Eds), tannins (D. G. Roux), and lignin (W. J . Schuberf),
which is biogenetically connected with tannins in carbohydrate metabolism. The glycosides and the aglycons of
flavones and flavonones are of pharmacologic interest, and
their toxicology and therapeutic use therefore receive critical
treatment. One finds a similarly good account of the influence of intestinal bacteria, nutritional factors, and dosage
on the products of metabolism and elimination. The hydrolyzable and condensed polyphenols of the tannins are
examined in a relatively short but informative section. Here
and in the chapter o n lignin, one encounters isocyclic polyhydroxy compounds, which occupy a central position in the
metabolism of aromatic systems, and which are aromatized
and - in the case of lignin - condensed into large, complex
polymeric molecules. Their chemical structure is mainly
hypothetical, and it is therefore too soon to discuss the
general features of these molecules. By contrast, the general
outlines of the biogenesis based on C02. carbohydrates, shikimic acid, and C3 fragments are known. The same applies to
the origin of methoxy groups and to the polymerization of
monomeric phenylacrylic acid precursors by enzymatic
oxidoreductase and peroxidase (laccase). The degradation by
fungi that decompose wood is first hydrolytic (even ether
bridges are cleaved here by etherases), and then oxidative,
leading to vanillin derivatives.
A monographic study of the biosynthesis of alkaloids and
other secondary nitrogen metabolites by J . E . Spenser represents the main part of the book. This subject is treated in
biogenetic terms, and, despite the great variety of the substances, the study shows the relations between the synthetic
pathways, which had been earlier proposed speculatively by
organic chemists, mostly exhibiting an extraordinary insight.
The syntheses involved are relatively simple (Mannich condensations and oxidative coupling of phenols), but give rise
to a remarkable group of compounds, which are difficult to
systematize.
One of the most fascinating chapters of the chemistry of
natural products is that of secondary fungal metabolism,
although the underlying principles are not clear since we do
not know whether we are dealing here with elimination
processes or with accumulation processes; nevertheless,
about 1000 compounds have so far been isolated. R . Bentley
and J. M. Campbell examine some routes for the aromatic
syntheses based on glycolysis intermediates, acetate, mevalonate, and polyoxomethylene compounds, together with the
formation of terpenes, sterols, and anthraquinones. The
enzymatic halogenation and the regulation of these processes
have also been described.
397
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