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Book Review Newer Methods of Preparative Organic Chemistry Volume II edited by W. Foerst translated from the German into English by F. K

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SELECTED ABSTRACTS
Bis-(4-hydroxyiminomethyIpyridinio)methyl ether dichloride
( I ) , a drug which reactivates acetylcholine esterase
inhibited by phosphoric esters, has been developed by A .
Liittringhaus and I. Hagedorn. According to clinical investigations carried out by W. D. Erdmann and H. Engelhard,
(I) acts as a n antidote to poisoning with esterase-blocking
alkyl phosphates and has a high therapeutic index. It shows
considerable superiority over reference substances and,
when given in greater doses, is capable of passing the bloodbrain barrier. It is obtained in 95 % yield by reacting pyridine4-carboxaIdoxime with cr,a'-dichlorodimethyl ether, and can
be obtained in the form of the syn- and the anti-oxime, m. p.
235 "C and 220 "C, respectively. Aqueous solutions of ( I )
are stable and can be injected intramuscularly. / Arzneimittelforsch. 14,1 , 5 (1964) / -De.
[Rd 9071258 IE]
Penicillamine nitrile was synthetized for the first time by I.
Ugi and E. Bottner. cr-Bromoisobutyraldehyde was treated
with NaSH and H C N in methanol. Subsequent addition of
CH2Nz and 85 % phosphoric acid gave a-hydroxy-P-mercaptoisovaleronitrile ( I ) in 88 % yield; b.p. of the hydrochloride 92-94 OC/4 mm.
f.H3
Br-C-CHO
I
CH3
NaSH
HCN
H37 ?H
HS-C-CH-CN
H37 P;JH2
HS-C-CH-CN
I
I
H 3C
H3C
(1)
(2)
Reaction of (1) with liquid NH3 gave penicillamine nitrile
(a-amino-9-mercaptoisovaleronitrile)(2) in 75 yield; m.p.
of the hydrochloride: 181-182°C. Compound (2) reacts
with aldehydes and ketones to form 4-cyano-5,5-dimethylthiazolidines. / liebigs Ann Chem. 670, 83 (1964) 1 -Ma.
[Rd 901/251 IE]
The synthesis of substituted benzoic acids, henzonitriles, and
benzaldehydes is reported by F. Effenberger and R. Gieiter.
These substances can be prepared from p-substituted N-alkyland N-arylbenzamides, the starting materials being readily
obtained in good yield by Friedel-Crafts reaction of isocyanates and benzene derivatives. Hydrolysis of N-substituted
benzamides, e.g. p-chlorobenzanilide, with alcoholic KOH
gives rise to p-substituted benzoic acids, e.g. p-chlorobenzoic
acid (yield = 91 %). Von Braun degradation of N-substituted
leads to nitriles,
benzamides, e.g. N-cyclohexyl-p-toluamide,
e.g. p-toluonitrile (yield 100 %). Sonn-Muller aldehyde syn2
thesis via the imidochlorides, which are reduced to Schiff
bases with SnC12 and subsequently converted into aldehydes
by hydrolysis with acid, was used to prepare some aromatic
aldehydes, especially ones that cannot be obtained by direct
formylation, e.g. p-fluorobenzaldehyde and 2,4-dichlorobenzaldehyde (obtained in 83 % and 61 yc: yield, respectively).
/ Chem. Ber. 97, 480 (1964) / -Ma.
[Rd 5/282 IE]
Keto-carotenoids in crustacea were detected by H. Thomman
and H. Wuckernagel. Flamingo feathers contain canthaxanthin as coloring matter; the carotenoid source is considered
to be their food, particularly small crustacea such as waterfleas (Daphnia). p-Carotene ( I ) , echinenone (2), and canthaxanthin (3) were isolated from various Daphnin species,
H2
(2) and (3) in large quantities. It is presumed that waterfleas oxidize p-carotene and accumulate (2) and (3). The
astaxanthin from flamingo feathers may be derived from (3). /
Naturwissenschaften 51, 87 (1964) 1 -De. [Rd 9061257 lE]
5,12-Diphenyl-7-oxyldinaphtho[l,2-b
:2',3'-d]furan (2) a new,
stable aroxyl radical has been described by D. Schulte-Frohlinde and F. Erhurdt. Oxidation of ( I ) (obtained from 1 hydroxy-4-phenylnaphthalene) with PbOz in benzene yields
the aroxyl radical (2), which is green in solution and forms
black crystals, m.p. above 192"C, in 50 % yield. According
t o measurements of their paramagnetic spin resonance, the
crystals contain about 15 % free radical, the solutions about
90 %. Solid (2) is stable to oxygen. Its degree of dissociation
and its sensitivity towards oxygen lie between those of
triphenylphenoxyl and tri-t-butylphenoxyl. I t is somewhat
superior to a,=-diphenylpicrylhydrazylfor trapping other free
radicals. / Liebigs Ann. Chem. 671, 84, 88 (1964) / -Ma.
[Rd 9031256 IE]
BOOK REVIEWS
Newer Methods of Preparative Organic Chemistry, Volume 11,
edited by W. Foerst, translated from the German into
English by F. K. Kirchner. Academic Press, New York and
417pp. Cloth-bound $ 14.50.
London. 1963. XV
+
Some 50 years ago, the editors of the 4th edition of Beilstein
had to acknowledge that it was impossible to encompass the
whole field of organic chemistry in a handbook of reasonable
timeliness. The past decade brought the same realization in
the much more restricted field of preparative organic chemistry. Houben- Weyl mushroomed from a modest handbook
of 4 volumes (4th edition, 1925) into a grandiose compendium
of the size of Beilstein and with all its merits, but also with
Angew. Chem. internat. Edit. / Yol. 3 (1964)
1 No. 8
the inevitable disadvantage of staying hopelessly behind the
rapidly advancing improvement of classical procedures and
the steady development of novel techniques. Nonetheless,
for generations to come, this impressive work will still remain
the starting point for any systematic search for the best
solution of problems in preparative ot-ganic chemistry. The
referee doubts, however, if future generations will ever dare
to compile another edition. Like Beilstein, which covers the
progress of organic chemistry in series of supplements, even
in this restricted field, the only possible solution providing a
steady, timely source of information is the publication of
specialized monographs by experts in individual fields. Long
before a new edition of Houben- Weyl could even be visualized,
595
this approach has been chosen all over the world and has
resulted in a large number of surveys and progress reports of
this kind.
A highly successful attempt in this direction was the innovation of “Neuere Methoden der Priiparativen Organischen
Chemie” edited by W. Foerst, the first volume of which
appeared during World War I1 as a collection of verbatim
reprints of articles originally published between 1940 and
1942 in “Die Chemie”. Thus, a unique combination of
timeliness and competence with a minimum of time-consuming editorial work was achieved which resulted in enthusiastic
acceptance of this volume everywhere. Its importance was
immediately recognized by the Allies who had it translated
into English and reprinted in several editions in the United
States.
After the war, as editor of “Angewandte Chemie” W. Fuerst
resumed publication of this popular series and presents in
the present volume authentic English translations of !he
fourteen articles comprising Volume I1 of the original
German edition, which appeared in 1960.
The contributions are again written by recognized authorities
in their fields. The selection of the individual chapters resulted
both from the personal interest of the editor and from the
availability of German specialists. A book of this kind can
hardly satisfy everybody, and what is missing from this
volume may reasonably be expected in future issues of this
series. However, even the highlq critical reader, will have to
admit that all the articles are well-presented, interesting,
exhaustive reports of the progress in their respective field.
Contrary to Volume I, which covered also mere techniques
such as chromatography and vacuum distillation, Volume I1
is strictly oriented towards the preparation of definite classes
of compounds. However, sometimes the impression is
obtained that too much has been included; procedures such
as the continuous preparation of phenylsodium and the alkylstion of phenols with low molecular-weight olefins under
pressure which require specialized expensive cquipment will
rarely appeal to the average laboratory worker for the occasional preparation of a compound. The individual chapters
deal mainly with the principles of various types of syntheses
and with thcir variations and applications. Reaction mechanisms are occasionally discussed, especially where their
understanding may allow the experimenter to extend the
scope of the reaction or vary its conditions rationally rather
than by intuition alone. Each chapter includes a generous
supply of detailed preparative directions for actual examples
in the style of Huuben- Wry.];these are adequate for reproduction without recourse to the original literature. The book
contains the following contributions, which have been brought
up t o date by the authors: Syntheses with Acetoacetaldehyde
(W. Franke, R . Kruft, K . Kossing); Preparation of Peptides
and Ureas Using Reactive Amides or Imides (St. GoldSchmidt, H. L. Krauss) ; The Preparation of Long-Chain
Carboxylic Acids from 1,3-Cyclohexanediones (H. Stetter);
Ethyl 2-Cyclopentanonecarboxylate and Its Importance in
Syntheses ( R . Mayer); Ketene in Preparative Organic Chemistry (G. Quadbeck); Preparative and Analytical Importance
of Phosphines and Related Compounds (L. Horner, H . Hoffmann); Reduction of Carbonyl Compounds with Complex
Hydrides ( H . Hurmann) ; Alkylation of Aromatic Amines
( R . Stroh, J . Ebensberger, H . Haberland, W. Hahn); Chemical Synthesis of Intermediates of Carbohydrate Metabolism
( H . 0. L. Fischer); Amidomethylation (H. Hellmarin) ; Selective Catalytic Oxidations with Noble Metal Catalysts ( K .
Heyns, H . Paulsen); Alkylalion of Phenols with Alkenes ( R .
Stroh, R. Seydei, W. Hahn); Continuous Preparation of
Phenylsocium (M. Ruschig, R . Fugmrinn, W. Meixner);
Newer Investigations on Oxidations with Lead Tetraacetate
( R . Criegee).
The author and subject indices compensate to a large extent the lack of systematic arrangement of the information
presented. Like its predecessor, the above volume will extend
the use of these extremely valuable monographs to chemists
not conversant with German. The organic chemist may rightfully consider this book indispensable, but any member of
the profession who is occasionally concerned with problems
of organic preparations will derive ample benefits from it.
C/z. Grundmrinn
[NB 182/86 IE]
Zwisehenprodukte-Tafeln.(Intermediates Tables), by 0. Horn.
Carl Hanser Verlag, Miinchen 1963. 1st Edit., 20 tables,
paperback, D M 7.80 (about $ 2.00).
The number of organic intermediates has grown enormously
in the past decades. These compounds, in addition to their
original application as dyestuff components, are meanwhile
used in many other fields. Petrochemistry has made it
possible to develop new syntheses of intermediates from
cheap raw materials so that the whole field is now extremely
difficult for the non-specialist to comprehend.
The present “Intermediates Tables”, based on lectures by the
author, render a valuable service in view of this situation. In
twenty tables, the essential routes of syntheses for the manufacture of intermediates are clearly presented in the form of
family trees. Starting from the raw materials methane,
acetylene, olefins, benzene, toluene, xylene, naphthalene, and
anthracene, the more important derivatives and their respective genetics are evolved. Thus, the entire range from
classical dyestuff intermediates to modern processes of olefin
chemistry is embraced. The reagents and characteristic reaction conditions are not always given for the individual process stages but could perhaps have been mentioned without
any great loss in clarity.
The “Intermediates Tables” is a kind of “organic chemical
technology without words” and will probably not only
facilitate students’ understanding of the subject but will
always be of service when a survey on this complex field is
W. Hahn
[NB 185/81 IE]
sought.
Anabole Steroide (Anabolic Stcroids). By H . L. Krriskewiper.
Biochemie und Klinik, monographs edited by G . Weitzef
and N. Zollner. Georg Thieme Verlag, Stuttgart 1963. 1st
edit.,VIII, 166 pp., 14 illustr., 14 tables,cardboard DM 38.(about $10.00).
With this monograph, the author presents a book, to which
one may ascribe the highest praise because of its potential to
induce the production of new works on this subject. His exhaustive survey of the abundance of experimental results is
supported by 1108 literature references. After a review of the
nomenclature, chemistry, and metabolism of anabolic steroids (19 pp.), their effects are described in detail (49 pp.). In a
further chapter (9, pp.) the effect ofanabolic steroids is compared with that of other anabolic hormones. The most important results on the problem of the structure and activity of
anabolic steroids as well as on their clinical use, contraindications, and side-effects are presented in detail and in review,
so that the book will be of great use equally to biochemists,
experimental clinicians, and physicians. The author indicates
numerous questions which still remain open. The reviewer is
certain that the book deserves a mark of thanks in many future
publications on this subject.
E. Gerhards [NB 187/82 IE]
Registered names, trademarks, e f c . used in this journal, even without specific indication ihereof, are not fo be considered unprotected by law.
0 1964 by Verlag Chemie, GmbH. - Printed in Germany by Druckerei Winter, Heidelberg.
All rights reserved. N o part of this journal may be reproduced in any form whatsoever, c.g. by photoprint, microfilm, or any other means, without
written permission from the publishers.
Editorial Olfice: Ziegelhauser Landstrasse 35, Heidelberg, Germany, Telephone 24975, Telex 04-61 855, Cable address: Chemieredaktion Heidelberg.
Chief Editor: W.Foerst . Editor: H . Griinewald.
Publishers: Verlag Chemie GmbH. (President Edzrard Kreuzhage), Pappelallee 3, Weinheim/Bergstr., Germany, and Academic Press Inc. (President
Walier J. Johnson), 1 1 1 Fifth Avenue, New York 3, N.Y., U.S.A., and Berkeley Square House, Berkeley Square, London, W. 1, England.
Correspondence concerning advertisements should by addressed to Vertag Chemie, GmbH. (Advertising Manager W.Thiel), Pappelallee 3, WeinheimBergstr., Germany, Telephone Weinbeim 3635, Telex 04-65 516. Cable address: Chemieverlag Weinheirnbergstr.
596
Angew. Chem. internat. Edit. f Voi.3 (1964) 1 No. 8
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