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Book Review Nuclear Magnetic Resonance Spectra and Chemical Structure. Vol. 1 The Spectral NMR Parameters of Compounds with Analyzed Spectra. By W. Brgel

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have liked to see a reference to the work of Brown and Djerassi 121, which forms a good supplement to this section of the
The work presented to date on the mass-spectrometric behavior of organic substances has shown that mass spectra are
determined by the heteroatoms and the functional groups.
In discussing mass spectra, the authors have therefore
classified the organic compounds according to their heteroatoms, as hydrocarbons and compounds of oxygen, nitrogen,
sulfur, halogens, boron, phosphorus, and silicon. I t is understandable that this classification is somewhat arbitrary if
several different heteroatoms are present in the molecule.
However, the index a t the end of the book simplifies the
search for a particular class of compounds.
The important characteristics necessary for identification and
structural analysis are here presented more forcibly than in
similar works, without necessarily a full discussion of the
mechanism by which the fragments are formed. The treatment covers not only the mass spectra of monofunctional
compounds, which gave a particularly clear picture of fragmentation, but also the mass spectra of polyfunctional compounds and natural products with complicated structures,
such as steroids. The methods of mass-spectrometric structure analysis are illustrated by numerous well-chosen examples. The possibilities and limits of the method are discussed in the concluding chapter, with reference to 17
examples .
Random checks have shown that the literature UI: to 1967
has not, after all, been covered completely. This limits to
some extent the use of the book as a reference work, as is
suggested by the text of the dust-cover. The book can be
recommended as an extensive introduction to organic mass
spectrometry and as a good introduction to mass-spectrometric structure analysis. H. F. Grltzmacher [NB 749 IE]
Chemie der Eiweisskorper, he Chemistry of Proteins). By
E. Waldschmidt-Leitz a
0 . Kirchmeier. Ferdinand EnkeVerlag, Stuttgart 1968. rd Edit., xi, 258 pp., 8 illustrations, 37 tables. Cloth-bound D M 57.00.
The long established work under review has been extended
by a few chapters to indicate the new developments that have
taken place since the publication of the 2nd edition. The
description of the synthesis and degradation of amino acids
in living organisms deserves especial mention. The reader is
given a good and concise review with ample literature
The book deals primarily with the classical chemistry of
amino acids (coherent treatments of this subject are hard to
find), with the synthesis, preparation, and structure analyses
of peptides, the properties of proteins, and elucidation of their
amino-acid sequences, and finally describes, in brief, a considerable number of proteins. Tn only a few instances would it
have been desirable to discuss new developments in greater
detail,e.g. the denaturation of proteins or the determination of
the tertiary and quaternary structures of proteins as they are
known today. All chapters are carefully supported by literature citations, which enables the student to deepen his understanding by contact with the original work. The book is well
produced and, as usual, the presentation is very clear; in all,
it is a very suitable reference work. H. Fasold [NB 760 I E ~
Atlas of Electron Spin Resonance Spectra. By B. H. J . Bielski
and J . M. Gdbicki. Academic Press Inc., London-New York
1967. 1st EM., xiii, 664 pp., numerous figures and tables,
bound, $ n.00.
A collection of ESR spectra has long been awaited by research
workers in this field. The two authors must be commended
for undertaking this laborious task of collecting spectra from
[2] Cf. P. Brown and C. Djernssi, Angew. Chem. 79, 481 (1967) ;
Angew. Chem. internat. Edit. 6, 477 (1967).
Angew. Chem. internat. Edit. Vol. 7 (1968) / No. 12
the widely scattered data in the published literature. The atlas
contains well over a thousand reproductions of ESR spectra
derived from paramagnetic species in solution, in gases, in
glasses, and in powders - but not, however, in single crystals.
The reproductions are neatly executed and well arranged.
Most of the spectra were published before the end of 1964;
only a few are taken from more recent or from unpublished
work. A certain selectivity limits the completeness of the
work, but increases its reliability. No attempt has been made
to verify the correctness of the data. Apart from the ESR spectra, ancillary information - such as the paramagnetic species,
their preparation, the recording conditions, and coupling
constants - is listed.
While the atlas largely comes up to our expectations, indeed
its usefulness has already been proved several times in the
reviewer’s laboratory, certain shortcomings should not be
overlooked. In the first place, the spectra have not been
selected carefully enough. This is particularly true of the
spectra of radicals that have been recorded under similar
conditions, without essentially differing from each other.
Such spectra could have been omitted, together with the line
diagrams showing the schematic hyperfine structure, which
are largely superfluous. The spin densities calculated from
the measured coupling constants using a somewhat arbitrary
proportionality factor are also unnecessary.
Frequent errors are found in the formulas of the paramagnetic species and in the coupling constants indicated.
For instance three different formulas are used for the three
spectra given for the ally1 radicals @p. 29 and 30):
CHz=CH-CH?; CH2=CH-CH2 + CHz-CH=CH*; and
H2C-CH-. CH2. They appear as different species; moreover, in the mesomeric notation the sign should be replaced
by the usual double-headed arrow (++).
The radical cation whose spectrum is reproduced on p. 538
was obtained from 1,3,6,8-tetraazapyrene and not from the
4,5,9,10-tetradeuterio derivative as quoted.
For the radical anion of pyrene the coupling constant of the
two equivalent protons in positions 2 and 7 is erroneously
given twice on p. 533 (aF = -1.09 G and up7 = 1.05 C ) .The
first value is correct, apart from the incorrect negative sign
which cannot be determined from the spectrum given.
The numerical indices of the coupling constants of the p nitrotoluene radical anion (p. 628, top) are meaningless, since
the numbering is missing on the corresponding formula. If the numbers are taken to be those normally used in
chemical nomenclature for p-nitrotoluene they are actually
When all is said and done, however, this atlas is a very useful
and commendable aid which every ESR laboratory should
posses. Nevertheless, a critical approach is indicated, and it
would be wise to consult the original literature at !he same
F. Gerson [NB 757 IE]
Nuclear Magnetit Resonance Spectra and Chemical Structure.
VoI. I: The Spectral N M R Parameters of Compounds
with Anaryzed Spectra. By W . Briigel. Academic Press,
New York-London / Dr. Dietrich Steinkopff-Verlag.
Darmstadt 1967. 1st Edit., xviii, 235 pp., loose-leaf,
$ 35.00.
In comparison t o the familiar “infra-red Briigel” the present
volume offers not just another spectroscopic method but an
entirely different selection. Whereas the older book was and is - an introduction, this work is almost exclusively a
summary, an ambitious atlas of spectra which no longer
merely lists the spectra themselves, as produced by the
spectrograph, but lists them in an extracted form.
To pass on to the form and content, it might be said that this
is not really a book at all, but rather a file of medium thickness in the A 4 format. The work is divided into an introduction in German and English (7 pp.) tables (212 pp., English
text), a bibliography (520 citations), and a n alphabetical subject index (English, about 2500 entries).
96 1
The part containing the tables is divided into two major
groups. The first deals mainly with substances in which only
the protons are capable of nuclear resonance, or in which
only proton resonance was measured, and the second,
relatively small, group contains data relating to nuclei other
than H. Inorganic substances and polymers are not considered except for isotactic polystyrene. The tables contain
the nuclear resonance parameters (chemical shift and coupling constants) of the particular substance, with the solvent
used, its concentration, and the literature reference. Only
those substances are listed whose spectra had been accurately
evaluated. The literature has been included up to 1966.
The alphabetical division into 88 basic substances and their
derivatives is very easy to refer to but in some cases a little
confusing. The tables under the heading ‘anthracene’ or
‘naphthaIene’ d o not contain all the data on thesecompounds;
the reader still has t o refer to the voluminous chapter on
benzene, under the subheading of ‘condensed aromatics’.
Numerous benzo compounds are listed under ‘benzene’,
while others - like benzimidazole, benzofurazan, etc. - are
listed under their own names. However, all the substances
are easily found in the subject index.
This work has been printed o n good, strong paper - a
necessary precaution if frequent use is envisaged. I t will be
very useful to anyone engaged in the practice of nuclear
resonance spectroscopy, not least because he can rely o n the
author’s critical treatment of the literature.
This work should be brought up to date from time to time.
Perhaps the recently published data on polymers could then
also be taken into account.
I). Humrnef [NB 758 IEI
The Chemistry pf Non-Aqueous Solvents. Vol. 1: Principles
and Techniques. Edited by J . J. Lugowski. Academic Press,
New York-London 1966. 1st Edit., xi, 403 pp., 18 figures,
6 tables, $ 16.50.
This book covers the more important aspects of reactions and
physical measurements in non-aqueous media - including
theoretical fundamentals - as well as the methods generally
used in investigations in low-boiling media and molten salts.
The following topics are treated: 1. Lewis acid-base exchange
in polar non-aqueous media (I). W. Meek); 2. Solvation of
electrolytes and solvent equilibria (E. Price); 3 . Acid functions in amphiprotic media ( R . G . Bates); Electrode potentials
in non-aqueous solvents ( H . Strehfow); 5. Solvent extraction
of inorganic substances (L. J. Kutzin); 6. Experimental techniques for low-boiling media (J. Nassler); 7. Experimental
techniques for the investigation of molten salts (R. A . Bailey
and G . J. Janz).
The first chapter is written in a fluent and easily understandable style. All essential aspects and modern points of view are
discussed. The reader is first familiarized with the out-ofdate concepts (e.g. SOClz as electrolyte in liquid SOz), which
are appropiately corrected in another part of the book. This
consideration of the historical course of the topic under
review is a n attractive and interesting feature of the work.
The reviewer would, however, have preferred the text to have
been based o n more modern and up-to-date knowledge and
the historical development to have been brought more into
the margin.
Section 2 contains a precise and clearly arranged treatment
of the influence of solvation on ionization equilibria. Modern
techniques of investigation are taken into consideration, e.g.
N M R measurements for the evaluation of interactions between cations and solvent molecules.
Section 3 is somewhat exacting and demands a great deal of
the reader. For example, the reviewer is of the opinion that
Zzmaifov’s ideas for the derivation of the solvation energy of
the proton is treated far too briefly. However, it must be
emphasized that the section as a whole is very clearly written.
Section 4 is written with remarkable didactic skill. Those who
are acquainted with the fundamentals of electrochemistry
and thermodynamics will have very little difficulty in under-
standing this contribution. The reader is given such a n excellent and impressive survey of the measurement and evaluation of electrode potentials in non-aqueous media that he
has no need to refer to the original literature.
The author of Section 5 has been confronted with the difficult
task of working through the extensive amount of original
literature concerning the separation of substances by distribution between two solvents. He has, however, succeeded in
compiling a representative review of the principles of the
many methods presently being used.
Section 6 is of immense value to all chemists who are concerned
with, or are likely to concern themselves with non-aqueous
solutions. The techniques used for preparation of solutions
are described mainly for lower-boiling media. Particular
interest attaches to solutions of solids o n which physical
measurements or chemical reactions are to be carried out.
All the physical methods that have become of importance in
the chemistry of non-aqueous solvents, e.g. polarography,
Raman spectroscopy, etc., are so treated that one can perform experiments as a rule without further ado, mainly
because of numerous and well illustrated figures of apparatus
and experimental set-ups that have been included.
The experimental side is also to the fore in Section 7; however, for a complete understanding of the fundamentals of
processes the necessary theoretical explanations are also
included. Methods for the determination of magnetic susceptibility, electrochemical and spectroscopic methods, and
methods for the investigation of transport phenomena are
treated, as are also and techniques such as calorimetry cryoscopy. Adsorption chromatography and chemical reactions
in molten salts are also dealt with.
All sections are supplemented with a fully comprehensive
bibliography. This work, which will appear in several
volumes, has closed a gap in the “secondary literature”. For
this reason, our thanks goes out to the editor, who has made
a name for himself particularly through his investigations o n
solutions in liquid ammonia. All chemists with a n interest, or
potential interest, in the field of non-aqueous solutions will
welcome the appearance of this work.
0 . Schmitz-Du Mont [NB 745 IE]
Halogen Chemistry. Edited by V. Gutmunn. Academic Press,
London-New York 1967. Volume 2: 1st Edit., xii, 481 pp.,
many figures and tables, 115 s; Volume 3: 1st Edit., xiv,
471 pp., many figures and tables, 115 s.
In this three-volume work on halogen chemistry the editor
gives a review of the present-day position of the subject. Unfortunately, the date of publication chosen is somewhat late,
for a number of the topics dealt with have recently been
treated in standard text books of fluorine chemistry and of
inorganic chemistry.
Volume 2 is concerned primarily with preparative chemistry
and with covalent halogen compounds; halogen oxides and
halogen acids have, however, been rather neglected.
Compounds of halogens with elements of the 3rd and 6th
main groups are likewise unconsidered.
This volume contains the following chapters: 1. SulfurNitrogen-Halogen Compounds (0.Glemser and M . Fild);
2. Fluorophosphoranes ( R . Schmutzler); 3 . Halides of Arsenic
and Antimony (L. Kolditz): 4. Inorganic Silicon Halides
(E. Hengge) ; 5 . Organoelement Halides of Germanium, Tin,
and Lead (J. Ruidich. H. Schmidbuuer, and H . Schumann);
6. Equilibria Involving Halide Complexes in Aqueous Solution (G. P . Haight jr.); 7. Halogenation and Halogen Exchange in Fused Salt Media ( N . R. Thompson and B. Tittfe);
and 8. Covalent Oxychlorides as Solvents (V.Gutmann).
The authors of the individual articles, who are undoubtedly
experts in their fields, have all contributed to the development of halogen chemistry by their own work.
In the first five chapters, structures, fluorine magnetic
resonance data, and a number of reaction mechanisms are
given, in addition to chemical properties and reactions. The
Angew. Chem. internat. Edit. / Vof. 7 (1968)/ N o . I2
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