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Book Review Anorgnische Chemie (Inorganic Chemistry) Volume III. By I

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cyanide as early as 1782 and even tested its “unusual odor and
taste” in complete unawareness of the toxicity of the compound. However, Scheele’s name will remain famous mainly
because of his discovery of oxygen around 1771, i.e. before the work of Priestley in 1774, although Scheele did not
publish his findings until later in his book “Chemische Abhandlung von der Luft und dem Feuer” (Chemical Discourse
on Air and Fire) in 1777. According to J. R . Partingtan a report on Scheele’s work had actually been published beforehand in 1775 by Bergman. “There can hardly be another
scientist”, writes Zekert, “who, within the brief span of only
two decades, has created something so meaningful and of lasting value as has Scheele”, and hence it now seems almost
incredible that all his scientific work was carried out within
the confines of a laboratory attached to his pharmacy.
The volume closes with a table giving a synopsis of the important dates in Scheele’s life in relation to world events of
that time. This book will perhaps induce its readers to interest
themselves further in this fascinating scientist and in the effects of his work on the development o f organic chemistry.
W. Ruske [NB 25711 15 IE]
Mass Spectrometry of Organic Ions. Edited by F. W. McLafferty. Academic Press Inc., New York-London 1963. 1st
Edit., xii f 730 pp., numerous illustrations and tables,
linen, $24.00.
In recent years mass spectrometry has assumed an important
position in chemical research. In this collective volume several
authors review their particular fields. The topics dealt with
are intended for chemists and physicochemists and include
both theoretical and practical aspects of mass spectrometry.
The result is a multifarious treatment that will be inspiring
and useful to all interested in the subject.
The sections on the quasi-equilibrium theory and appearance
potentials are written clearly and with discerning criticism.
Several instructive chapters are devoted to the application of
mass spectrometry to the study of ion-molecule reactions,
free radicals, electrical discharges, and flames, and abundant
data are given on experimental techniques, equipment, and
previous results. A section on the mass spectra of negative
ions is also included.
The second part of the book, which is dedicated to the correlation of mass spectra with molecular structure, will undoubtedly be of greatest interest to the organic chemist. A
brief but excellent recapitulation of the general principles involved is followed by chapters in which the techniques
and results of mass spectrometry are illustrated by way of
examples. Investigations of numerous fatty esters made it
possible to detect the fragmentation paths and to elucidate the
structures of some natural products. Extensive studies of alkylbenzenes revealed very surprising information about the
structures of some ions. Both chapters distinguish in exemplary
fashion between proven and postulated fragmentations.
The next section (on the elucidation of the structures of amino
acids and alkaloids) illustrates how complicated natural
materials can be successfully investigated by combining chemical and mass-spectroscopic results. The success in studying
complex mixtures of similar compounds is demonstrated by
taking petroleum as a n example. A section o n high-resolution
spectrometers indicates the vast potentials of this method.
The chapter o n terpenes is unfortunately not satisfactory. In
contrast to the rest of the book, here the individual compounds are dealt with too summarily; the fragmentations are
few and are all unproved. In addition, there are several errors
here, e . g . the fragmentation of myrcene o n page 653.
On the whole, however, the book is to be highly recommended.
Its individual articles are excellent and describe the whole field
of mass spectrometry; repetitions have been almost invariably
avoided. The literature has generally been evaluated till spring
1962. All results and findings have been critically reviewed;
this and the abundant use of tables and illustrations deserve
particular praise.
W. Benz [NB 254/112 IE]
176
Air Chemistry and Radioactivity. By C. E. Junge. International
Geophysics Series, Vol. 4, edited by J. van Mieglienz. Academic Press, New York-London 1963. 1st Edit., xii +
382 pp., 83 figs., 66 tables, linen $ 13.50.
Publications o n the chemistry of the atmosphere are scattered
throughout many scientific journals. The author is therefore
to be highly commended for this survey of the present state
of research on this subject, which is now developing rapidly.
The concentrations of oxygen, nitrogen, and most of the inert
gases in the atmosphere can be regarded as being constant
with respect to space and time, and hence are not dealt with
in the book. The distributions with space and time of the
other gaseous components of the atmosphere - over a dozen
are known - are described (Chapter 1). These data are important not only because of their influence on organic life
(e.g. owing t o their absorption of sunlight), but also for the
investigation of atmospheric circulation and exchange processes. In the second chapter, the physical and chemical properties of aerosols are discussed, together with their distribution in the troposphere and stratosphere. Aerosols have the
property of concentrating material from their environment in
various ways, and so their structure and composition are continuously changing; they are largely responsible for atmospheric static, atmospheric optics, cloud formation, and the
chemistry of the atmosphere.
The most important rainfall processes, which are responsible
for the clearing of the atmosphere, are nucleation within
clouds and scrubbing by rainfall underneath the clouds. There
are also numerous other processes by which materials can be
removed from the atmosphere: sedimentation, fixation by
objects o n the earth‘s surface, adsorption of gases, chemical
reactions, and escape into outer space. General rules for these
processes are derived here from a large number of observations (Chapter 4). The most important topic in this connection is the chemical composition of rainfall.
Impurities in the air are mainly due to industrial factories and
roadway traffic. I n the fifth chapter, a general discussion on
the composition of these impurities, their distribution, and
their removal from the atmosphere is given. Atmospheric
radioactivity is discussed in the third chapter; this arises from
three sources: the natural radioactivity of the earth’s crust,
which leads to the emanation of radon and thoron, the radioactive isotopes produced in the upper troposphere and lower
stratosphere by cosmic rays (of these, 14C and 3H have acquired particular importance), and the nuclides formed by
nuclear explosions, which are now of general interest because
of the danger of radiation damage due to radioactive fall-out.
Much attention is given to a description of the distribution
of these isotopes in the atmosphere and of their importance
for studying circulatory and separatory processes.
This book by Jirnge links together chemistry, nuclear chemistry, and meteorology. It will provide a valuable aid to all
scientists interested i n problems associated in the widest sense
with the atmosphere.
W. Groth [NB 260/118 IE]
Anorganische Chemie (Inorganic Chemistry), Volume 111. By
I . Naray-Szabd. Akademie-Verlag, Berlin and Verlag der
Ungarischen Akademie der Wissenschaften, Budapest
1963. 1st Edit., pp. 669, 21 illustr., 4 tabl., linen D M 48.(about $12.00).
With this third and last volume, the German edition of “Anorganische Chemie” is now completed. The first three chapters deal with the metals and compounds of the copper, zinc,
and gallium groups and the fourth, very extensive chapter is
devoted to the chemistry of the iron and platinum groups of
metals. In addition, the rare gases are discussed, and the rare
gas fluorides and oxygen-containing xenon compounds discovered during the last two years are mentioned. A comprehensive account of the properties of the elements and a short
section o n geochemistry and cosmic chemistry complete this
volume.
Angew. Cfieni.internot. Edit. / V d . 4 (1965)
1 No. 2
As in the preceding volumes [ I ] the author has compiled with
remarkable care much physical data and extensive chemical
factual material. Unfortunately, especially in the chapter on
the metals of group 8 of the periodic q s t e m , this is not always
up-to-date and outmoded structures and formulae are given,
e.g. for cyano complexes and halogenocarbonyls. Many new
types of compounds of the iron and platinum metals have not
been mentioned, e.g. the reader will search in vain for a reference t o sandwich compounds of the ferrocene type or to the
numerous co-ordination compounds of these metals with
anomalous oxidation numbers which have been isolated and
structurally analysed during the last fifteen years and which
are of bonding and sterochemical interest. On the other hand,
many a compound stated t o be “non-existent” could have
been left out. Despite these reservations and certain deficiencies i n the coverage of the latest developments, the third
volume of Nuray-Szabd will also serve its purpose as a handbook in many instance?. Its carefully compiled subject and
formula indices contribute significantly t o its efficiency.
R . Nnst INR 218/88 lE]
Friedel-Crafts and Related Reactions. Edited by G. A . Oluh.
Vol. I : General Aspects. Interscience Publishers, a Division of John Wiley & Sons, New York-London 1963.
1st Edit., X X X I V i- 1031 pp., numerous illustrs. and
tables, linen f; 11.0.0 (about S 30.50).
Volume I of this series of four volumes (6 books with about
4000 pp.) begins with a survey over the vital, even dramatic
period around the discovery of the reaction, which is particularly well illustrated by numerous facsimile reproductions, including extracts from the laboratory notebooks
written together by Friedel and Crafts. (Chapter I: G. A . Oluh
and R . E. A . Dear). I n Chapter 11, G. A . Oluh defines the
range and limitations of the “Friedel-Crafts and Related
Reactions” (120 pp.) thereby including any substitution
reaction, isomerization, elimination, cracking reaction, polymerization, or addition that is catalysed by Lewis or protonic
acids. - This is followed in Chapter H I by a short but
poignantly lucid discourse by R. J . Gillespie on ‘‘Brmsted
and Lewis Acids” in which the influence of structural parameters upon the acid strength and the importance of strong
protonic acids as solvents is stressed. - Under the heading
“Catalysts and Solvents” in Chapter IV, G. A. Oluh no
longer describes simply Lewis acids of the metal halide type
but includes metal alkyls, metal alkoxides, acidic oxides and
sulfides, cation exchangers, and even cation-forming substances such as AgC104 or AgBF4 in his scheme without
constraint. A detailed discussion is given of the part that
cocatalysts play in Friedel-Craft reactions; here the importance of small amounts of water or oxygen is given particular
attention.
The role of Lewis catalysts in non-aqueous systems is dealt
with by M . Bauz and V. Gutmann in Chapter V. One of the
particularly valuable features of this chapter is t o be found
in its orderly tabular collection of reactions given with the
Lewis acid used, the solvent employed, the ionization of the
donor-acceptor complex, etc., which is probably unmatched
elsewhere. - In Chapters VI and VII, the coordination
compounds of boron halides and aluminum halides are
discussed respectively by D . R. Marfin and J. M . Canon.
Although the authors are t o be awarded due commendation
for the admittedly arduous task of compiling a summary, for
example, of all the boron halogen compounds known (one
table contains no less than 464 compounds!), it would
probably be more beneficial to the ease of surveyance of the
complete work if this chapter (150 pp.) were either radically
abbridged or - even better - reorganized to appear as a
separate monograph for those interested in this topic.
Chapter VIII by G. A. Oloh and M. W. Meyer again makes
good reading, for it records all the intermediates of FriedelCrafts reactions known t o date. The intelligibility of this
chapter I S aided to n o mean extent by the exact definitions
[I] Cf. review of Vols. I and I1 in Angew. Chem. 75, 695 (1963);
Angew. Chem. internat. Edit. 2, 404 (1963).
Angew. Chem. internot. Edit. / Vol. 4(1965)
1 No. 2
given of %-, 0-,and n-complexes, which arise by the interaction of the following coreactants a) catalyst/cocatalyst,
b) catalystlsubstrate, c) catalystlreagent, d) catalyst/product,
and e) catalystkolvent. The profound knowledge of the
editor in this field in particular makes possible a critical
appraisal of chemical and physical methods for detecting
such intermediate complexes. In supplementation, Chapter IX
-by D. Cook gives a summary of spectroscopic experiments
designed to convey information o n the nature of the donoracceptor complexes occuring as intermediates in FriedelCrafts reactions. This description includes, for example, the
complexes of ketones, which are formed as reaction products,
with Lewis acids and the complex formation of Lewis acids
with solvents (e.g. nitrobenzene). It is understandable that
the major accent has been placed upon nitronium and acylium
ions and their complexes, for these are relatively easy to
secure and are very important. Here again well presented
tables enable the reader to obtain a good idea of the current
status of knowledge, which, however frequently needs confirmation by other independent methods, particularly X-ray
crystallography.
In Chapter X, R . M . Robert and G. J . Fonken describe vividly
how labelled compounds have been applied with great profit
in the field of Friedel-Crafts reactions for mechanistic studies,
particularly of technically interesting alkylations, dealkylations, rearrangements, and fragmentations. I n comparison
with the abundance of experimental material, the theoretical
evaluation of the results, which is built u p on a remarkably
critical attitude, is rather scant. - I n Chapter XI on “Reactivity and Selectivity”, G. A . Oloh shows that the overall
effect of a catalyst/cocatalyst system must always be regarded
as the complex result of a number of combining and opposing
factors, including the different electronegativities of the
halogeno ligands in Lewis acid halides, the dissociation
energies of dimeric metal halides, the electronegativities of
the molecules acting as donors, the bond lengths and strengths
within the donor-acceptor complexes, lattice and solvation
energies, and steric effects. This chapter in particular can be
consulted by the reader with profit, for it is one of the richest
and gives empirical sequences for the relative reactivities of
catalysts, cocatalysts, acyl halides, erc. in the most important
types of reaction. If a compound contains more than a single
reactive group, then Friedel-Crafts reactions are subject t o
considerable limitations on account of the frequently observed lack of specificity of the Lewis acids used. Numerous
cleverly selected examples are given to illustrate the various
possibilities for procuring a selective course of a FriedelCrafts reaction on polyfunctional compounds. Both the
theorist and experimenting chemist will be interested by the
detailed treatment given in this connection t o questions of
the positional selectivity observed in electrophilic substitutions
of aromatic compounds.
A brief introduction t o the thermodynamic approach to
Friedel-Crafts reactions is given by D.R.Stulf in Chapter XII.
Calculations o n the course of ten reactions - mainly alkylations and acylations - are presented and will enable the
organic chemist who is not fully competent in this field to
find easy access t o the subject, especially since complicated
reactions have been wittingly- avoided and all the thermodynamic constants required for the operations are presented
in orderly tables in the appendix. - - The carbonium ion
mechanism for the Friedel-Crafts reaction, which proabably
enjoys general acceptance today, finds additional support in
the more or less complete racemization observed when the
corresponding optically active alkylating agents are used.
The none too numerous findings that have been accumulated
t o date from stereochemical studies in this field have been
admirably collected together by H . Hart in the last chapter,
which fortunately waives any all too broad theoretical
background.
It is certainly to be expected that this first volume of the
series, which is so good as to make its user look forward t o
the coming volumes, will assume its merited and indispensible
position in academic and industrial laboratories.
[NB 298/157 IE]
J . Gosselck
177
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