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Book Review Analytiker Taschenbuch. Band 1. (Analytical Pocketbook. Vol. 1). Edited H. Kienitz R. Bock W. Fresenius W. Huber and G

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to react with 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-Fj-~glucopyranosylamine (2)"'a,61in the presence of ethyl 2ethoxy-l,2-dihydroquinoline-l-carboxylate
(EEDQ)['].
The structure of (3a) and (3b) is confirmed by IR and
'H-NMR spectroscopy. The selective cleavage of the Peocprotecting group proceeds quite smoothly in a ca. 5% solution of diethylamine in tert-butyl alcohol.
HNEt2
(30)
IBu-OH
COOC HzCsHS
I
HzN-C H
I
I
AcO-,
C OOC HzC 6HS
I
Peoc- L e u - NH-CH
y Hz
FHz
C=O
A c O i
C=O
Peoc-Leu4H
(41
NH-Ac
(5)
NH-A c
After 30 minutes at room temperature, (3a) affords the
crystalline deblocked benzyl 4-N-glycosylasparaginate(4)
in 67% yield. Under these conditions the primary ester at
C-6 of the glucosamine is not attacked.
In the case of glycosyl peptides the Peoc-protecting
group has three advantages in comparison to the frequently employed benzyloxycarbonyl (Z)-moiety :
1) In the case of a Z-protected compound analogous to
(3a), the hydrogenolysis leads to unselective deblocking of
the N- and C-terminals""].
2) During the basic cleavage of the benzyl ester in the
presence of the Z-group the 0-acetyl groups are reAt the same time there is the likelihood of rearrangement in the asparagine moiety-as is also likely under acid conditions[71.
3) N-Glycoside coupling via Z-aspartic anhydride and
hence separation of the desired 4-amide from the 1-amide
of the aspartic acid formed in the same way can thus be
avoided['l.
In the case of (3a), not only selective cleavage of the
Peoc-protecting group is possible but also hydrogenolytic
deblocking of the C-terminal with intact ester groups on
the carbohydrate moiety.
The peptide chain can be elongated on the free amino
group of (4); thus, with Peo~-leucine[~~,
e. g. in dichloromethane in the presence of EEDQ, the Peoc-glycodipeptide
ester (5) can be synthesized in ca. 60% yield.
Experimental
(3a): To a solution of (la)[31(6.7 g, 12 mmol) in anhydrous CHCl, (80 ml) cooled to -10 to -5°C are added
first a solution of (2) (4.2 g, 12 mmol), likewise cooled to
- 10 to -5"C, and then solid EEDQ (3.26 g, 13.2 mmol).
The mixture is stirred overnight and allowed to warm to
room temperature. The solution is then washed three times
each with 50 ml 0 . 5 HCI
~
and with H 2 0 , and dried over
Na2S04; after removal of the solvent under reduced pressure, the crude product is chromatographed on 300 g of silanated silica gel, 70-230 mesh (Merck), with chloroform/methanol (25 :I). Yield 7.2 g (65%), amorphous, decamp. : 100- 110 "C.
(4): A solution of (3a) (6 g, 6.5 mmol) in tert-butyl alcohol (150 ml) is treated with a 20Y0solution of diethylamine
in tert-butyl alcohol and the mixture stirred for 30 min at
room temperature. After removal of the solvent under reduced pressure the residue is taken up in 100 mL of
CH2CI,, washed three times with 50 ml of water and dried
over Na,S04. Renewed evaporation of the solvent and recrystallization from chloroform/ether affords 2.4 g (67%)
of crystalline, analytically pure (4). m.p. 149-150°C
(dec.).
Received: March 20, 1981 [Z 884b IE]
German version: Angew. Chem. 93, 918 (1981)
CAS Registry numbers:
(la), 79134-86-4; (Ib), 79134-87-5; (Z), 4515-246; (3a). 79134-88-6; (36).
79134-89-7: (4), 79134-90-0; (5). 79134-91-1; Peoc-Leu-OH, 73951-87-8
[I] A. Gortschalk: Glycoproteins, 2nd edit., Elsevier, Amsterdam 1972.
121 Cf. a) H. G. Garg, R. W. Jeunlor, Carbohydr. Res. 52, 246 (1976); b) ;bid
70, 47 (1979).
[3] H . Kunz, Chem. Ber. 109, 2670(1976); Angew. Chem. 90, 63 (1978); Angew. Chem. Int. Ed. Engl. 17, 67 (1978).
141 a) G. S. Marks. R. D. Marshall. A . Neuberger, Biochem. J. 87, 274 (1963);
b) A. Neuberger, ibid. 32, 1435 (1938).
[SI a) D. Belleau, G. Malek, J. Am. Chem. SOC.90, 1651 (1968); b) D. Dunstan, L. Hough. Carbohydr. Res. 23, 17 (1972).
[6] C. H. ~ O f r o n R.
.
W. Jeanfoz, J. Org. Chem. 28, 3228 (1963).
171 a) A. Yurnumoto, C. Miyashita. H . Tsukarnoto, Chem. Pharm. Bull, 13,
1041 (1965); b)A. R. Battery, J. C. Robinson, J . Chem. SOC.1955, 259.
[8] H . G . Garg, R . W. Jeanloz, Carbohydr. Res. 23, 437 (1972).
BOOK R E V I E W S
Anaiytiker Taschenbuch. Band 1. (Analytical Pocketbook.
Vol. 1). Edited H . Kienitz, R. Bock, W. Fresenius, W. Huber and G. Tolg. Springer-Verlag, Berlin 1980. vii, 439
pp., bound, DM 78.00.
If, as is planned, a volume of the "Analytiker Taschenbuch" actually appears every two years, the analytical
community can truly congratulate itself, particularly if the
high level of the publications can be maintained. The great
novelty value lies-in that apart from the subdivision into
Fundamentals, Methods, and Applications there is no
scheme of structure and treatment laid down beforehand
and references are made to current needs. The editors have
been able to secure the services of well-known and excellent authors and to achieve a high standard.
896
In the Fundamentals, the chapter on sampling, data
processing, and evaluation methods must be specially singled out. The Methods section is particularly valuable because of the clear nomenclature in electrochemical processes, corresponding to the IUPAC rules, the exhaustive
tables for gas chromatography, and-for the air-monitoring environmental analyst -a summary of the testing tubes
available for monitoring working premises and for industrial gas analyses. Also noted with pleasure is the introduction to chiroptical methods and, particularly, the table of
Cotton effects covering many examples.
It is likewise appropriate to mention the valuable hints
on sources of error in measurements with ion-selective
electrodes. Of modern physical methods of analysis, a very
Angew. Chem. Ini. Ed. Engl. 20 (1981) No. 10
good chapter on X-ray spectral analysis in SEM has been
included. The methodological part is completed by a contribution on surface analysis, which-with the exception of
the now widely used ATR-FT-IR methods-gives an excellent review of this important field.
The third part, dealing with application techniques, begins with a relatively new but increasingly important field,
enzymatic analysis, and shows how widespread the direct
determination of various substances with comparatively
specific enzymes in the presence of complex mixtures has
already become. Since there is no doubt about the extreme
importance of the determination of mycotoxins, and especially aflatoxins, the corresponding contribution, made
more valuable by the schemes of analysis, is greatly welcomed. It will prove particularly valuable for the foodstuffs and feedstuffs researcher. The qualitative investigation of dyestuffs as such and on the fiber has undoubted
practical importance.
Methods of detecting and determining environmentally
relevant products and compounds are now in constant demand, and this has been taken into account. Thus, in addition to methods for the detection of narcotics and dopes,
the determination of mercury compounds (including organomercury compounds) in water and the analysis of plutonium are given.
Summarizing, volume 1 of the pocketbook is indeed heterogeneous. It is also very informative and up to date, and
the chemists and analysts not dealing directly with the individual subject fields now have at their disposal a very
valuable guide.
Hanns Malissa [NB 548 IE]
X-Ray Analysis and the Structure of Organic Molecules. By
J. D . Dunitz. Cornell University Press, Ithaca 1979, 528
pp., bound, E 33.00.
Dunitz’s monograph is based on a series of lectures and
is therefore very personal in style and presentation. For
this reason alone, it is worth reading. This naturally also
applies to its contents, which are organized in two large
sections, crystal structure analysis (I) and molecular structures (11), relieved by historical observations on the development of X-ray structure analysis. Diffraction, symmetry,
methods of structure determination, refinement processes,
and above all treatment of the results are dealt with in Part
1. The direct juxtaposition of theory and practise, instead
of a chronological exposition, is particularly successful.
The detailed examples thus make the material understandable even to readers with little mathematical training. Part
I1 is not just a compilation of results, but begins with a
unique reference to the aspects decisive for the chemist
that can be demonstrated from the wealth of known molecular structures. The sections on structural analysis and
chemistry, electron density in molecules, topological limitations in cyclic systems, and treatment of conformations
with symmetry groups open up a fascinating field of molecular events far beyond that achievable by drawings of
molecules and statements of distances.
The book may be recommended most heartily to anyone
who would like to know how molecular structures are determined and what can be deduced from them apart from
their topology. The author is evidently a great admirer of
the method and its results. The reviewer would agree that
“cooking” is not the only way to bring chemically relevant
knowledge to light.
Hans Georg von Schnering
Angew. Chem. In[. Ed. Engl 20 (1981) No. 10
[NB 549 IE]
The Heterocyclic Chemistry of Phosphorus. Systems Based
on the Phosphorus-Carbon Bond. By L. D . Quin. John
Wiley & Sons, Chichester 1981. xiii, 434 pp., bound
f 27.05. -ISBN 0-47 1-06461-0
The Inorganic Chemistry of Biological Processes. By M. N.
Hughes. John Wiley & Sons, Chichester 1981. 2nd edit.
ix, 338 pp., bound, E 9.90.-ISBN 0-471-27815-7
Annual Reports on Fermentation Processes. Vol. 4. Edited
by G. T. Tsao. Academic Press, New York 1980. xiv, 319
pp., bound, $ 28.50.--ISBN 0-12-040304-8
Chromatographic Science Series. Vol. 14. Introduction to
Analytical Gas Chromatography. History, Principles,
and Practice. By J. A . Perry. Marcel Dekker, Basel 1981.
xviii, 426 pp., bound, SFr. 74.00.--ISBN 0-8247-1537-3
Electron Spin Resonance. Vol. 6. Senior Reporter: P. B.
Ayscough. The Royal Society of Chemistry, London
1981. xiii, 359 pp., bound, E 49.00.-ISBN 0-85186-8100.-A volume in the series “Specialist Periodical Reports”
Pergamon Series in Analytical Chemistry. Vol. 1. An Introduction to Chemical Equilibrium and Kinetics. By L.
Meites. Pergamon Press, New York 1981. xiii, 549 pp.,
bound, $ 19.95.--ISBN 0-08-023803-3
Advances in Heterocyclic Chemistry. Vol. 27. Edited by A .
R . Katritzky and A . J. Boulton. Academic Press, New
York 1980. ix, 331 pp., bound, $ 49.50.-ISBN 0-12020627-7
Analytical Sciences Monographs No. 8. The Sampling of
Bulk Materials. By R. Smith and G . V. James. The Society of Chemistry, London 1981. viii, 191 pp., bound, E
16.50.-ISBN 0-85186-810-X
Molecular Interactions. Vol. 2. Edited by H . Ratajczak and
W. J. Orville-T%omas. John Wiley & Sons, Chichester
1981. xxiii, 627 pp., bound, L 39.00.-ISBN 0-471-276812
The Chemistry of Functional Groups. The Chemistry of the
Sulphonium Group. Part 1 and 2. Edited by C. J. M .
Stirling. John Wiley & Sons, Chichester 1981. xiv, 847
PP-7
Grundlagen der Verfahrenstechnik und chemischen Technologic. Modellierung von Phasengleichgewichten als
Grundlage von Stofftrennprozessen. Edited by K. Hartmann, W. Schirmer. and M . G . Slinko. Acadernie-Verlag,
Berlin 1981. xviii, 419 pp., bound, DM 87.00
897
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