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Book Review Handbuch der Arzneimittel-Analytik (Handbook of Drug Analysis). By S. Ebel

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Table 1. Reaction of I-hexene with Et2MeSiH and CO [a].
Catalyst [mmol]
(WI)
(Z)-f2j
(E)-f2)
c ( 2 1 [.I
["/.I
7
9
13
16
6
10
44
58
56
43
70
59
45
24
23
25
22
24
89
82
79
68
92
83
Product distribution [%]
R ~ d C 0 ) 1 2(0.4)
RhCI(PPh& (0.4)
RhCI(PPhj)3 (0.4) + Et3N (1.0)
Coz(C0)a (0.4)
C O ~ ( C O(0.4)
) ~ + nBu3P (1.0)
C O ~ ( C O(0.4)
) ~ + Ph3P (1.0)
40
41
88
57
18
77
[a] Reaction conditions: 1-hexene (30mmol), EtlMeSiH (lOmmol), CO (50kg/cm2), and catalyst in benzene (20ml),
140"C, 2Oh.
[b] Determined by GLC.
[c] Proportion of straight-chain enol ethers (Z)-(Z j plus (E)-(Zj as determined by GLC in overall product.
isomers in the overall product of analogous hydroformylations
of I-hexene are 89.6 % and 62.4 %, re~pectively[~]).
These results clearly suggest that the new catalyzed reactions
of olefins with hydrosilanes and carbon monoxide have basic
features closely resembling those of hydroformylation.
Experimental :
A solution of 1-hexene (3.7 ml, 30mmol), diethyl(methy1)silane (1.02g, IOmmol), triethylamine (0.1 g, 1 mmol), and
RhCI(PPh& (0.37g, 0.4mmol) in benzene (20ml) is placed
in a 100-ml stainless steel autoclave. The autoclave is flushed
with N2 (50 kg/cm2) and CO (50 kg/cm2), then charged with
CO (50kg/cm2)and heated at 140°C with stirring. After 20h,
the autoclave is cooled and depressured. Analysis of the
.reaction mixture by GLC (Silicon OV-1, 5 % , on Uniport
KS, 6 m, 115"C) with an internal standard (n-tetradecane,
RRT (relative retention time)= 1) showed it to contain enol
silyl ethers [@)-(I
), RRT=0.36; ( E ) - ( I ) , 0.39; (Z)-(2),0.45;
(E)-(2), 0.601 and disiloxane [(Et2MeSi)z0,RRTz0.191 in
88 % (total) and 11 % yields, respectively. The relative yields
ofthe enol silyl ethers are shown in Table 1. Analytical samples
were obtained by fractional distillation (b.p. 105-1 15 "C/12
torr) followed by repeated preparative GLCL6'.
1670 cm-' (C=C); 1.50 (d, CH3C=C), 1.83 (m, CH2C=C), 5.92 (s,
HC=C). ( Z ) - ( 2 ) , 1660 cm-' (C=C); 1.96 (m, CH2C=C), 4.30 (dt, J = 6
and 8 Hz, CH=COSi), 6.02 (d, J = 6 Hz, C=CHOSi). (E)-(2), 1660 cm-'
(C=C); 1.80 (m, CH2C=C), 4.80 (dt, J = 12 and 6 Hz, HC=COSi),
6.08 (d, J = 12 Hz, C=CHOSi).
Comment on the Publication Entitled "Synthesis of
a Stable 1,3,4-Dio~azolidine''~~~
By Gerwalt Zinner and Helmut B l a s s ~ ]
Contrary to the authors' assumption, compound ( I ) described by Varwig and Mews[']is not the first (stable)derivative
of this ring type, correctly designated 1,4,2-dioxazolidine,since
the set of locants 1,4,2 is lower than 1,3,4. The adamantanone
derivate (2)"' and the bicyclic derivative (3)13] were reported
live years ago.
Received: September 2, 1977 [Z 847 IE]
German version: Angew. Chem. 89, 919 (1977)
[l] Transition Metal Reactions of Silanes, Part 4.-Part 3: Y Seki, S. Murai,
1 . Yamamoto, N . Sonoda, Angew. Chem. 89, 818 (1977); Angew. Chem.
Int. Ed. Engl. 16. 789 (1977).
[2] 1: Seki, A . Hidaka, S . Murai, N . Sonoda, Angew. Chem. 89, 196 (1977);
Angew. Chem. Int. Ed. Engl. 16,174 (1977); Y Seki, A . Hidaka, S. Makino,
S . Murai, N . Sonoda, J. Organomet. Chem., in press.
[ 3 ] J. Falbe, Carbon Monoxide in Organic Synthesis. Springer-Verlag. Berlin
1970; F . E. Paulk, Catal. Rev, 6,49 (1972);L. Marko in R. Ugo: Aspects
of Homogeneous Catalysis, Vol. 2. D. Reidel, Dordrecht 1974, p. 1.
[4] D. Evans, J . A. Osborn, G. Wilkinson, J. Chem. SOC.,41968, 3133.
[5] E. R . Tucci, Ind. Eng. Chem. Prod. Res. Dev. 9, 516 (1970).
[6] The IR (neat) and NMR (CCIJ data are: (Z)-(I ), IR 1670 cm-' (C=C);
NMR 1.48 (d, CHsC=C), 2.00 (m, CH2C=C), 5.90 (s, HC=C). (E)-(l),
Received: November 8, 1977 [Z 865 IE]
German version: Angew. Chem. 89, 920 (1977)
p]
Prof. Dr. G. Zinner, H. Blass
Institut fur Pharmazeutische Chemie der Technischen Universitat
Beethovenstrasse 55, D-3300 Braunschweig (Germany)
[l] J. Varwig, R . Mews, Angew. Chem. 89, 675 (1977); Angew. Chem. Int.
Ed. Engl. 16, 646 (1977).
[2] G. Zinner, B. Geister, Chem.-Ztg. 96, 693 (1972); the data given are
supplemented by the mass spectrum (70eV, 170°C): m/e=329 M + (lo),
179 (loo), 162 (loo), 150 (90); we are grateful to Dr. H . - M . Schiebel,
Gesellschaft fur Biotechnologische Forschung, Braunschweig-Stockheim,
for recoding the spectrum.
[3] G . Eikelmann, W Heimberger, G . Nonnenmacher, W M . Weigert, Justus
Liebigs Ann. Chem. 759, 183 (1972).
BOOK REVIEWS
Handbuch der Arzneimittel-Analytik (Handbook of Drug Analysis). By S. Ebel. Verlag Chemie GmbH, Weinheim-New
York 1977. 1st edit., x, 417 pp., 3 figs., 354 tables, plastic
binding , DM 118.-.
This new handbook differs from the earlier works on drug
analysis in that first place has not been given to the analytical
procedure with subsequent treatment of the substances appear882
ing in the various fractions. Instead, extensive lists of analytically important data are provided for some 600 drugs. The
division of the material into pharmacologically important
groups is both novel and useful. In the first place the user
can obtain an impression of the substance in question from
the medical information that is almost always known for
a drug, but he can also see, without a time-wasting search,
Angew. Chem. lnt. Ed. Engl. 16 (1977) N o . 12
what method of identification or quantitative determination
will be most useful in a given case. The number of important
cross references could be increased; in the case of hypnotics,
for example, there is no reference to benzodiazepines.
The clearly tabulated information about the drugs provides
an unusual wealth of individual data. These range from the
formula, name, salts, molecular weight, identification reactions,
UV spectra, and solubilities to chromatographic behavior
and possible methods of quantitative determination. In these
tables the methods of chromatography (qualitative and quantitative TLC, GC, HPLC) are treated in special detail, in line
with their importance.
Welcome too are the numerous indications of possible
sources of error, e.g. the warning that identical Rf values
of a sample and a reference substance do not constitute proof
of identity.
The book leaves no room for criticism as regards its scope
or its topicality. Its value in the future depends on how rapidly
it can be updated in later editions to reflect the steadily
changing range of products on the market. Already some
of the materials included (e.g . Aminorex and Iproniazid) are
no longer manufactured.
Supported by 2000 references to the literature, the work
is a “Handbook” in the true sense. In spite of the high price
it can be recommended without any reservations as a reference
work in analytical laboratories and for supplementing the
practical exercises in the study of pharmaceutical analysis.
Norbert Kreutzkamp
[NB 392 IE]
Thermochemical Kinetics. Methods for the Estimation of Thermochemical Data and Rate Parameters. By S. W. Benson,
John Wiley & Sons, Inc., New York 1976. 2nd edit., xi,
320 pp., 15 figs., bound, $ 28.50.
This is a considerably expanded second edition of the very
condensed collection, first published in 1968, of formulas and
approximation methods for estimating essential thermodynamic data and kinetic parameters for reactions taking place
in the gaseous state.
In the intervening years the monograph has earned a place
as a standard work. Its particular value lies mainly in the
numerous and logically arranged examples of calculations
and in the large number of numerical examples reproduced
in the text and in a special Appendix.
In the new version the material of the second chapter
(Methods for the Estimation of Thermochemical Data) is
expanded into six new sections which deal with the compensation effect and with radicals. As reworked, the third chapter
is devoted solely to unimolecular reactions, and a new section
on the Arrhenius parameters for bimolecular and termolecular
reactions has been added.
Chapter 5 (Analysis of Complex Reaction Systems) has
been extended by a further section (Steady-State Hypothesis);
in an Appendix there is a new table of ionic and atomic
polarizabilities. With these additions the book constitutes a
very useful source of information to all chemists who have
to consider the thermal and kinetic parameters of gas reactions
in their work.
The author has taken the trouble to work the large number
of new experimental results in the field into his second edition.
As an experienced practical chemist he has decided, for the
time being, to retain the calorie as the unit of energy and
to limit the recalculations into SI units to a brief indication.
This will make it much easier for the user to evaluate the
data in the literature.
Angew. Chem. Int. Ed. Engl. 16 (1977) No. 12
The book is well produced. Its importance is such that,
in spite of its price, it deserves the wider availability that
would follow from a German translation.
Theodor Ackermann [NB 387 IE]
Rompps Chemie-Lexikon(Rompp’sChemical Dictionary). Vol.
6: T-Z. By 0 . - A .Neumiiller. Franckh’sche Verlagshandlung
W. Keller & Co., Stuttgart 1977. 7th edit., 660 pp., +16
pp. Appendix, 135 figs., bound, DM 160.--.
The present volume 6 of this lexicon. which begins with
0 and ends with zyto, completes the 7th edition. The author
took a full five years to work through the 30000 key words,
and it paid off. Right up to the last volume one can sense
the editor’s effort to bring the keywords into line with the
most recent state of the art (it is by no means uncommon
to find references from 1976). Many keywords appear for
the first time; some such are transition state, overvoltage,
twistane, trifluoromethanesulfonic acid, and triforine. Depending on its specific importance, text that has grown too large
has been pruned to a sensible length, other parts have been
adjusted to the state of the science. The transition elements
are now given 3.5 columns, whereas previously 9 lines were
considered sufficient.The contribution on ultrasound has been
considerably expanded, as also has been the one on vinyl
chloride that recently came into the news. Where useful, structural formulas have been added (e.g. for Xylenol Blue).
Remarkable also are the changes among industrial products:
many new names appear and many have vanished. The tabular
review of the sources of vitamins is very clear.
The last volume contains additionally an Index Appendix.
This consists of a formula index by the Hill method and
an index of English and French expressions with their German
equivalents, the French part being distinctly slimmer than
the English with its ca. 8000 terms.
There is much evidence of the meticulous care taken by
the author, the collaborators, and the publisher in this production. One would only like to know that these praiseworthy
efforts have proved worthwhile, and the publisher and the
author can only learn this if as many colleagues as possible
use Rompp, collect suggestions for the next edition, and do
not forget to send them to the publisher. In such a rapidly
changing field as chemistry this must be considered well in
advance.
Christian Weiske [NB 390 IE]
Rare Gas Solids, Vol. 11. Edited by M . L. Klein and J . A .
Venables. Academic Press, London 1977. xi, 610-1252 pp.,
bound, i 26.00.-ISBN 0-12-413502-1
Contemporary Quantum Chemistry. An Introduction. By J .
Goodisman. Plenum Press, New York 1977. x, 375 pp., bound,
$ 39.00.--ISBN 0-306-30947-5
DIN Deutsches Institut fur Normung e. V.: English Translations
of German Standards 1977. List Including the Announcement of December 1976 in “DIN-Mitteilungen”. Beuth Verlag GmbH, Berlin 1977. 200 pp., paper.
883
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