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Book Review NMR of Chemically Exchanging Systems. By J. I. Kaplan and G. Fraenkel

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[3]
[4]
[5]
[6]
[7]
ences cited therein: b) A. Rieker, G. Henes, S . Berger, ibid. 108. 3700
(1975); cf. therein, the preparation of oxepin derivatives in analogy to
the azepine synthesis.
For more about ipso-attack see e . 9 . R. B. Moodie, K . Schofield. Acc.
Chem. Res. 9. 287 (1976); P. B. D.d e la Mare, ibid. 7, 361 (1974).
Review: D. Seebach. Angew. Chem. 91. 259 (1979): Angew. Chem. Int.
Ed. Engl. 18. 239 (1979).
H. H. Eckhardt, H . Persf. Tetrahedron Lett. 1979, 2125, and references
cited therein.
For analogous 1.2-additions to 2.5-cyclohexadienones cf. J. Bracht, E. L.
Dreher. A . Rieker. H. P. Schneider in Houben- Weyl-Miiller: Methoden
der Organischen Chemie, 4th edit., Vol. V11/3b. Thieme, Stuttgart 1979,
p. 746; cf. also [2b].
3 :2 mixtures of cis-trans isomers with preference for the components
with cworientation of methoxy and amide groups.
181 Review, e . 9 . . H. Perst: Oxonium Ions in Organic Chemistry, Verlag
Chemie, Weinheim-Academic Press, Weinheim and New York 1971, p.
131.
191 This formal reversal of the acylaziridine-oxazoline rearrangement via a
benzimine-cf., e.g , H. C. uan der Plaas: Ring Transformations of Heterocycles, Vol. I, Academic Press, New York 1973, p. 66-could occur,
because (6) is favored in an ultimate benzimine-azepine equilibrium, cf.
Ill[lo] Cf. the structure of the I-phenoxycarbonyl-IH-azepine:H . J. Lmdner.
B. uon Gross. Chem. Ber. 105, 434 (1972), and references cited therein:
the amide-N-C8 bond is at an angle of 15.8” to the plane through
NC2C7.
[ I I] The temperature dependence of the NMR spectra can be interpreted in
terms of the diastereomerization by rotation about the amide N-CO
bond, cf. [ I a].
BOOK R E V I E W S
NMR of Chemically Exchanging Systems. By J . I . Kuplan
and G . Fraenkel. Academic Press, New York 1980. xi,
165 pp., $ 19.50.
The concept of a quantum-mechanical density matrix,
introduced by Johann (John) von Neumann some 50 years
ago, is widely regarded as an advanced subject. Apart from
the classic works of Abragarn and of Slichter. written by
and for physicists, it has rarely made its way into textbooks
on N M R spectroscopy; of those addressed to the chemist,
many d o not condescend to mention it at all. And that in
spite of the fact that the density matrix formalism is not
only indispensable for a genuine understanding of relaxation and exchange phenomena in NMR, but is also used
routinely, by means of “canned” computer programs, in
applications especially to exchange problems. A monograph which purports to fill this gap would thus appear to
be a highly welcome addition to the N M R textbook literature.
Provided that it succeeds in its stated aim. The overwhelming impression on a first reading is that of an excessively formal treatment. About 70% of a typical page in the
main body of the text, which is principally concerned with
exchange, with one chapter on relaxation thrown in for
good measure, is taken u p by mathematical symbols; more
precisely, there are no less than 1045 equations all told,
squeezed into 162 pages of text. There probably exist readers who take delight in such a wallowing in formalism, but
one wonders at their frequency. The typical needs of a
nonspecialist would in this reviewer’s opinion be better
served by a concise presentation designed to exhibit the
logical transparency of the theory. Such a compact and
modern formulation does in fact exist, but the authors
have chosen to follow their own predilections.
As an unavoidable consequence of this heavy emphasis
o n formalism, the physical content of the theory and its applications get short shrift. The opportunity of counterbalancing the overdose of mathematics by a copious use of
well-designed figures has remained largely unexploited.
There are preciously few in the first place, and the majority
are moreover trivial o r uninformative. Lineshapes are frequently displayed as freehand drawings, and drawn with a
shaky hand to boot. Quite the worst example of its kind
has been selected by the publisher to disgrace the cover of
Angen. Chrrn Inr Ed Engl
20 I14811 No N
the book. One single page is devoted to experimental problems, which is of course totally inadequate. The authors
acknowledge the necessity of using a computer for actual
calculations, but no information is provided about where
to obtain the relevant programs or how to use them. Readers wishing to learn about how to apply the formalism to
the study of permutational mechanisms in the presence of
molecular symmetry, which ranks among the chemically
most exciting applications of the theory, are left out in the
cold. The possibility of using group-theoretical techniques
for simplifying the calculations is ignored. The citation
policy is strangely selective; references to papers of marginal relevance are sometimes listed at great length, whereas
there are gaping omissions otherwise. The carelessness in
assembling the references is also reflected in the numerous
misspellings and misquotations. As long as this fate only
befalls some of the lesser luminaries, a kind of excuse may
perhaps be concocted for the authors’ sloppiness, but
when it comes to names such as Wangsness, McConneN,
Hoffman, even the patience of an indulgent reviewer begins to wear thin. It is particularly sad to notice that Erwin
Hahn, one of the early pioneers, is not spared the indignity
of seeing his name perverted to Holm, in the references as
well as in the text.
Users of N M R spectroscopy wishing to educate themselves about density matrix methods are advised to turn to
other sources, especially to articles in the modern review
literature. Since they are not cited in the book, the authors
of four of them, all excellent, are mentioned here: P. D.
Buckley, K . W. Jolly and D. N. Pinder (1975); R. L. Vold
and R. R. Vold (1978); S . Szymanski. M . Witanowski and
A . Gryff-Keller (1978); A . Steigel (1978). The attention of
specialists is drawn to the SNOB (selective neglect of bilinear terms) technique, which is based on the authors’ original research. Although information about that topic can
also be extracted from the journal literature, it is convenient to have it between the covers of a book. This is an interesting idea, whose potential for applications has hardly
been tapped, but which holds great promise for the future.
It is the part of the book which the present reviewer found
worthwhile enough to read more than once.
0 Verlag Chemre GmbH. 6940 Wemherm. 1981
Gerhard Binsch
0570-0833/81/0808-0701 $ 0 2 50/0
[NB 545 IE]
701
Standards in Absorption Spectrometry. Edited by C . Burgess and A . Knowles. Chapman & Hall, London 1981.
xii, 142 pp., bound, L 9.50. - ISBN 0-412-22470-4
Gmelin Handbuch der Anorganischen Chemie. SpringerVerlag, Berlin 1981. 8th Edit. U-Uranium. Erganzungsband Teil A: Das Element. xxvii, 297 pp., bound, DM
732.00. - ISBN 3-540-93429-4
Atmospheric Pollution. By A . R . Meetham, D. W. Bottom,
S. Cayton, A . Henderson-Sellers and D . Chambers. Pergamon Press, New York 1981. 5th revised Edit., xi, 232 pp.,
bound, $ 15.00. - ISBN 0-08-024002-X
Low Temperature Properties of Polymers. By 1. Perepechko.
Pergamon Press, New York 1980. ix, 301 pp., bound, $
40.00. - ISBN 0-08-025301-6
Grundlagen und Anwendungen der Mossbauer-Spektroskopie. By D. Barb. Akademie-Verlag, Berlin 1980. x, 468
pp., bound, ca. DM 73.00
Berichte. Band 5/80. Umwelt- und Gesundheitskriterien fur
Quecksilber. Issued by the Umweltbundesamt. Erich
Schmidt Verlag, Berlin 1980. 140 pp., bound, DM
29.00. - ISBN 3-503-01868-9
Thermal Electrocyclic Reactions. By E. N . Marvel/. Academic Press, New York 1980. ix, 422 pp., bound, $
51.00. - ISBN 0-12-476250-6
Line Coincidence Tables for Inductively Coupled Plasma
Atomic Emission Spectrometry. Vol. 1 and 2. By P. W. J.
M . Boumans. Pergamon Press, New York 1980. Looseleaf $ 250.00. - ISBN 0-08-026243-0
Organic Reaction Mechanisms. Edited by A . C . Knipe and
W. E. Watts. John Wiley & Sons, Chichester 1981. 759
pp., bound, X 58.00. - ISBN 0-471-27818-1
Chemie des Bauwesens. Band 1. Anorganische Chemie. By
K . Krenkler. Springer-Verlag, Berlin 1980. xviii, 494 pp.,
bound, DM 88.00. - ISBN 3-540-10107-1
Progress in Surface Science. Vol. 9. Edited by S. C . Daoison. Pergamon Press, New York 1981. 268 pp., bound, $
93.00 - ISBN 0-08-026052-7
Spectroscopic Properties of Inorganic and Organometallic
Compounds. Vol. 13. Senior Reporters D. M . A d a m and
E. A . V. Ebsworth. The Royal Society of Chemistry, London 1980. vx, 413 pp., bound, E 66.00. - ISBN 0-85186113-X - A volume in the series “Specialist Periodical
Reports”
Liquid Phase High Pressure Chemistry. By N . S. Zsaacs.
John Wiley & Sons, Chichester 1981. vii, 414 pp., bound,
L 33.00 - ISBN 0-471-27849-1
Chemistry and Physics of Carbon. Vol. 16. Edited by Ph. L.
Walker, Jr. and P. A . li”lrower. Marcel Dekker, New
York 1981. xii, 322 pp., bound, SFr. 95.00. -ISBN 08247-6991-0
Advances in Catalysis. Vol. 29. Edited by D. D. Eley, H.
Pines and P. B. Weisz. Academic Press, New York 1980.
xiv, 367 pp., bound, $ 45.00. - ISBN 0-12-007828-5
The Carbohydrates. Edited by W . Pigman and D. Horton.
Academic Press, New York 1981. 2nd Edit., xxiii, 984
pp., bound, $ 69.50. - ISBN 0-12-556351-5
Analytische Methoden zur Priifung gesundheitsschadlicher
Arbeitsstoffe. Edited by D. Henschler. Verlag Chemie,
Weinheim 1980. Band 112. Luftanalysen. 322 pp., looseleaf DM 118.00. - ISBN 3-527-25857-4; Band 2/3.
Analysen in biologischem Material. 145 pp., loose-leaf,
DM 106.00. - ISBN 3-527-25858-2
Regwered names. rrodenmrks. erc used 1 ) ~rhis joernol.
Materialien. Band 6/80. Der Fall Kepone - Wirkungen
eines Schadstoffes auf die Umwelt. Issued by the
Bundesumweltamt. Erich Schmidt Verlag, Berlin 1980.
66 pp., bound, DM 24.80. - ISBN 3-503-01896-4
Corrigendum
The following corrections should be made to the short
communication entitled “The Unusual Stereochemistry of
the Cycloaddition of Vinyl Ethers with Sulfonyl Isothiocyanates” by Ernst Schaumann, Hans-Gunther Biiuch, and
Gunadi Adiwidjaja, Angew. Chem. Int. Ed. Engl. 20, 613
(1981):
On p. 614, left-hand column, the table caption “Ylides”
should read “Yields”.
On p. 614, right-hand column, *JOs and 2J,,,z, in lines
eight and nine should read ’$#, and 3Jl,on5, respectively.
On p. 614, right-hand column, in the last sentence “. . .
between cumulated n-electron systems ...” should read
“. .. between non-cumulated n-electron systems ...”.
even withour specific rrrdtmiron rhereo/, ore tior lo be
romtdered mprotecred
hj laa
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702
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