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Book Review Reactive Molecules. The Neutral Reactive Intermediates in Organic Chemistry. By C. Wentrup

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analytical inventiveness; he reduces methods, instruments,
and variations with impressive names and confusing abbreviations to the fundamental physical phenomena on
which they are based.
Basically, an electrical measurement is the common
characteristic of potentiometry, coulometry, voltammetry,
chronopotentiometry, and amperometric and galvanic
analysis. Gas chromatographic detection that depends on
electrical conductivity (flame ionization detector, thermionic detector, photoionization detector) and fi absorption (electron capture detector and helium detector) are
also mentioned in this context. Scintillation measurements
are dealt with under this heading as are fi-backscattering
methods, electron diffraction, electron spectroscopy (electron spectroscopy for chemical analysis, ultraviolet photoelectron spectroscopy, Auger electron spectroscopy,
electron impact spectroscopy), and the variants of mass
These methods are described in varying depth according
to their significance. Under thermochemical methods, besides differential thermal analysis (DTA) and differential
scanning calorimetry (DSC), calorimetry/enthalpimetry
and the measurement of heats of adsorption and thermal
conductivity are dealt with in adequate detail. The final
chapter is devoted to methods involving phase changes:
turbidity, micellar and solution titrations, the determination of salting-out curves and the precipitation curves of
polymers as well as phase solubility analysis.
The reader repetitively experiences the feeling that “the
penny has dropped” when he realizes that very different
procedures are based on similar physical principles-and
this is quite a desirable effect from the educational point
of view. The arrangement of the book facilitates understanding and learning. The section on “electrical” methods
is preceded by a chapter dealing with the fundamentals of
electronics (from ampere to operational amplifier). The descriptions of methods are arranged clearly; a historical
summary is often appended. Areas of application and the
possibilities of error are critically indicated. Without losing
sight of the significant, an abundance of information is introduced in tables, sketches and diagrams. The text remains readable thanks to the consciously frugal use of abbreviations. Numerous clear examples make plain the
practical applications of analytical work. Each chapter is
accompanied by a carefully selected and organized literature section, which enables quick access to original literature.
“Methods of Analytical Chemistry” will be much appreciated as a German language textbook by advanced students of analytical chemistry. For those working in the
field, it may serve as a reference work designed to deepen
their knowledge, and will be of particular use when a general index will be available with the final volume.
Jiirgen Auffurth [NB 693 IE]
Bundesanstalt fur Arbeitsschutz,
Dortmund (FRG)
Reactive Molecules. The Neutral Reactive Intermediates in
Organic Chemistry. By C. Wentrup. Wiley, Chichester
1984. xi, 333 pp., bound, L 33.20.--ISBN 0-471-87639-9
Professor Wentrup’s book provides a delightful and authoritative survey of the chemistry of neutral organic reaction intermediates. After a lucid presentation of basic notions concerning reaction kinetics, thermochemistry, and
frontier MO theory in Chapter 1, the author discusses the
Angew. Chem Ini. Ed. Engl. 25 (1986) No. 3
various classes of highly reactive molecules in a very readable fashion: radicals in Chapter 2, biradicals in Chapter
3, carbenes and nitrenes in Chapter 4, strained ring compounds in Chapter 5, and cyclobutadienes in Chapter 6.
The section on radicals, which includes an introduction to
the use of ESR and CIDNP, and the section on the chemistry of carbenes and nitrenes, which is especially well
done, are about three times the length of the others.
Throughout, the emphasis is on chemical reactivity rather
than the details of matrix-isolation or transient spectroscopy. Indeed, some of the reactive intermediates have only
been characterized by trapping reactions so far. Each
chapter concludes with a useful set of problems, including
information permitting the reader to consult the original
literature to check the answers.
The text contains a number of useful tables and up-todate references. Those given in Chapter 1 are primarily to
monographs and reviews, those given in Chapters 2-6 are
mostly to original literature. They number from about fifty
to well over two hundred per chapter. References to specialized monographs, at least one of which exists for every
chapter, are also provided and will be useful to readers
seeking in-depth information.
In spite of its general excellence, the book does contain
a few errors. Some are trivial and barely worth mentioning,
such as ‘‘AHO(sub1) for styrene” on p. 5, which should read
“for stilbene”, or the presence of charge on formula 161
on p. 113, which is not compatible with the rest of the
equation, as well as the overabundance of hyphens, the
only clue which gives away the author’s continental background (as in “in the gas-phase”).
A few other errors are more likely to mislead a novice.
The equation for u N ,on p. 38 does not make it clear that
spin densities on the neighboring atoms as well as that on
the atom i need to be considered; on p. 88 one might get
the impression that a more exothermic reaction is always
faster; on p. 110 the relation of LUMO energies to electron
affinities as determined from electron transmission spectroscopy and electron photodetachment spectroscopy
could have been included in addition to the mention of UV
spectroscopy (whose use for the determination of LUMO
energies is not straightforward); on p. 128 and 129 transition states are referred to as maxima rather than saddle
points on surfaces; on p. 163 S, is a singly excited and Sz a
doubly excited configuration; the arguments offered to account for the inaccessibility of the cyclobutadiene dianion
on p. 312 could be applied equally well to the easily accessible cyclooctatetratene dianion.
It should also be noted that the correlation energy of
two electrons is not the energy required to bring them into
the same orbital (p. 163, 176), that the “heavy atom effect”
normally does not refer to the mass of the collision partner
in collision-induced intersystem crossing (p. 183), that the
internal bond of a propellane does not tend to have a zero
electron density (p. 299), and that a triplet ground state is
not expected for square cyclobutadiene (p. 3 I0,3 16; cf. dynamic spin polarization). Finally, although the occurrence
of rapid tunneling between the two rectangular forms of
cyclobutadiene may eventually indeed be excluded by
photoorientation results as claimed on p. 319, our experiments are still underway and until the final verdict is in, a
conclusion is premature (Ref. 34c does not exist).
All of the shortcomings I noted above are of a theoretical or physicochemical nature and somewhat peripheral to
the main subject of the book, which is treated in a very
nice manner. For those interested in the preparation and
chemical properties of the uncharged reactive interme295
diates of organic chemistry, the book is to be recommended very highly indeed. I plan to use it in advanced
undergraduate and graduate teaching of organic chemistry.
Josef Michl [NB 697 IE]
Department of Chemistry
University of Utah
Salt Lake City, Utah 84 112 (USA)
Mammalian Semiochemistry. The Investigation of Chemical
Signals Between Mammals. By E. S . Albone. Wiley, ChiChester 1984. xii, 360 pp., hardback, f 29.50.-ISBN 047 1- 10253-9
It has really been known for a very long time that there
are signal agents (semiomones) that affect the behavior of
mammals. Yet natural product chemists and biochemists
were initially more interested in insect pheromones, which
are perhaps of greater economic significance. Albone’s excellent study shows how the unknown and often still mysterious world of signal agents has only recently begun to
be investigated with the modern instrumental analytical
techniques of natural product chemistry. A distinction is
made between substances used for communication by
mammals with one another and those used by mammals to
communicate with other species in their environment (allelochemicals).
The second chapter of the book shows comprehensively,
e.g. in the description of vapor analysis, the advances that
have been made and the progress that new techniques will
enable in the scientific investigation of the chemical ecology of mammals. It quickly becomes clear how complex is
the chemistry of an emotionally charged remark like “he’s
in bad odor with me” when a list of 135 substances in human perspiration is presented. Not only hydrocarbonsunsaturated and branched-alcohols, ketones, acids, esters, aromatics and heterocycles were identified, but also
compounds containing sulfur and even chlorine, such as
dichlorobutane. When Albone discusses the semiomones of
apes, elephants and predators, we can see that man is
“only” a mammal, since we find more o r less the same
chemistry every time. The organs for producing and storing allomones give the author the opportunity to extend
the treatment to cover allelochemicals. The significance of
the skin as a particularly environmentally sensitive organ is
indicated and reference is made to all glands that produce
odors and, above all, to the urine. It’s “imprinting power”,
even that of the less volatile components, is admirably discussed.
In the final chapter G. Shirley deals, briefly but very informatively, with the mammalian olfactory system, so restricted compared with that of insects. The author includes
a discussion of the manner of information transfer in the
olfactory nerves.
In every regard, Albone’s book is a successful presentation of an area of natural product chemistry whose significance is steadily increasing. It is to be hoped that the book
will find a wide readership amongst students, teachers, and
those engaged in research.
Hermann Schildknecht [NB 708 IE]
Organisch-Chemisches Institut
der Universitat Heidelberg (FRG)
Oligonucleotide Synthesis. A Practical Approach. Edited by
M . J . Gait. IRL Press, Oxford 1984. 232 pp., stitched,
X 11.00.-ISBN 0-904147-74-6
This book provides a concentrated introduction to oligonucleotide synthesis. Modern methods of D N A synthesis
and analysis are introduced by competent authors in individual chapters. The following topics are comprehensively
described: the preparation of protected synthetic units,
solid phase synthesis by the phosphate triester and the
phosphite triester methods, the purification of synthetic
oligonucleotides by HPLC and polyacrylamide gel electrophoresis and sequencing by the mobility shift and MuxamGilbert methods. These are supplemented by chapters on
newer methods for the synthesis of shorter oligoribonucleotide sequences and the interesting enzymatic synthesis
of oligoribonucleotides. Each chapter contains a comprehensive introduction followed by a detailed experimental
section which also supplies suggestions on obtaining reagents and equipment. The book scarcely offers anything
new to the experienced nucleotide chemist but is an excellent introduction for those who are looking for the quickest possible experimental access to this class of natural
products. An appendix provides such practical directions
as are necessary for oligonucleotide synthesis by those
with little chemical experience, e.g. the packing of silica
gel columns, TLC on silica gel, distillation at atmospheric
pressure and in vacuo and the packing of HPLC columns.
Here the book is clearly intended for those who have only
studied chemistry as an ancillary subject. However, it is
questionable whether the “fundamental chemical techniques” presented in this book would equip, say, a biochemist or a physician sufficiently to carry out manual oligonucleotide synthesis. For those using a DNA synthesizer, however, it could supply the necessary chemical background information. The book can be recommended to all
those who need a modern, straightforward introduction to
oligonucleotide synthesis.
Hubert Koster [NB 707 IE]
Institut fur Organische Chemie und
Biochemie der Universitiit Hamburg (FRG)
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