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Chemical Synthesis of Human Blood Group B Antigenic Determinant Type 2 Tetrasaccharide.

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In addition to the bands at 1250 cm-', the IR spectrum of
(7) and (8) contain weak v(C0) absorptions at 1720 and 1740
cm I, which are attributable to partial replacement of S by
0 (v(Ni S) of (6): 338, 267 cm-').
The electrical conductivity of the compressed powders
(6)-(8) are comparable with corresponding values for neutral or anionic "metal dithiolenes"['I; the resistance of the
powders shows the same temperature dependence as semiconductors.
Polymer
Electrical conductivity at 20 "C
8[n - ' cm-'1
(6)
s x l o - 4
I 7)
I&
6x10
3x10
'
'
Given a parallel arrangement of the chains in (6)--(8), interactions could occur between the metal atoms of neighboring chains which suggest electron delocalization perpendicular to the chain direction. A similar structure was recently
suggested for a Nil'-tetrathionaphthalene complex with semiconductor properties['].
layers (3i,O:-) is noted[']. A similar situation is encountered in the concatenation of individual (SO: -) tetrahedra
to give chain-type anions: ortho- and disilicates are common,
but trisilicates are much rarer. We have now succeeded in the
first synthesis and characterization of a tetrasilicate.
Ag,,Si,O,, was obtained by reaction of the binary components Ag,O and SiOz (low-temperature quartz) under oxygen pressure as a homogeneous, vermilion, moisture-insensitive powder [P(O,)= 2-4.5 kbar, T= 500-600 "C, I = 1-3
d]. None of the neighboring phases Ag,Si,O, (I)[21 and
Ag,Si,O, (11)[31 having a slightly higher silver content was
detectable in the product. Crystals could be grown starting
from the binary oxides in a silver nitrate melt by a previously
described methodI4I using an oxygen pressure of ca. 4.5 kbar
at 600 " C .
AglOSi4OI3
forms triclinic crystals, space group PILs1.The
Si-0 distances in the tetrasilicate anion (Fig. 1) vary between 158.9 and 168.3 pm, with average values of 161.6 pm
for terminal and 165.0 pm for bridging bonds; the three
Si- 0 Si angles are 146.5, 137.7, 128.4".
Received: February 15, 1979 [Z 216 I€]
German version: Angew. Cbem. 91. 499 (1979)
CAS Registry numbers:
(I). 70247-53-9; (Ib). 702247-55-1; (lc), 70247-57-3; (2). 70247-58-4; (3), 7024759-5: ( 4 4 , 70247-60-8 (4b), 70247-61-9; (S), 70281-08-2; (61, 70355-35-0; (7).
70281-09-3; NiCI,, 7718-54-9 Na,PdCI,, 13820-53-6; K,PtCI,, 10025-99-7.
(PhCN)2PtCI,, 15617-19-3
[ I ] J. S. Miller, A. J. Epstein, Prog. Inorg. Chem. 20, 1 (1976).
121 R. Allmann. T Debaerdemaeker. K. Mann, R. Matusch. R. Schmredel, G.
Seitz, Chem. Ber. 109. 2208 (1976).
[3] W Hieber, M. Cscheidmeier. Chem. Ber. YY, 2312 (1966); E. Lindner, R.
Grimmer, J. Organomet. Cbem. 25, 493 (1970); H. Laufen, B. Meyn, K . G.
Steinhauser, D. Vogel. R. Kramolowsky, ;bid. 112, C34 (1976); H. Weher, R.
Mattes, Chem. Ber. 112. 95 (1979).
[4] R. R. Schumaker, E. M . Engler, J . Am. Chem. Soc. 99, 5521 (1977); H. Poleschner, w. John, G. Kempe, E. Hoyer, E. Fanghanel, Z . Cbem. 18, 345
(1978).
[S] a) W. Beck, F. Gdtzfried. M. W. Chen, Chem. Ber. 1 1 1 , 3719 (1978); b) M
Hubenschuss, B. C. Cerstein, J. Cbem. Phys. 61, 852 (1974); J. A . C. uan OoQen, J. Reedrjk, Ahstr. Pap. XVIII. Int. Conf. Coord. Chem.. Prague 1978, p
95; A. Weiss, E. Riegler, personal communication; c) cf., however, R. West, H.
J, Niu, J. Am. Chem. SOC.X S , 2589 (1963); C. J. Long, Inorg. Chem. 17.2702
(1978); J. T. Wrobleski, D. B. Brown, ibid. 17, 2959 (1978); d ) D. Coucouuanis,
D. G. Holah, F. J. Hollander. ibrd. 14, 2657 (1975).
[6] PARTMModel 170 Electrochemistry System; lo-' M solution of (S) in 0.1 M
(n-C,H,),N ' CIO; in CH,CI,: Pt sheet as working electrode. reference electrode: Ag/AgCI in CH3CN. We are indebted to Prof. H. Noth and Dr. R.
Schwrthofer for the electrochemical measurements.
[7] E. V. Putton, R. West, J . Phys. Chem. 77, 2652 (1973).
[XI 10 M solution of C,S,K, in 0.1 M NaCIO,; dropping Hg electrode. reference electrode: standard calomel electrode.
[9] B. K. Tea, F. Wudl, J. J. Hauser, A . Kruger, J. Am. Chem. Soc. 99, 4862
(1977).
Fig. 1. Structure of the S1,01:' anion in the silver salt
L .
'
Ag,,Si,O,,-The
The apparent preference for certain kinds of silicate anions could be attributable to the fact that most of the known
structures are those of minerals formed under conditions in
which the variety of available cations was limited by geochemical selection. Thus, it cannot be ruled out that synthetic approaches may lead to further unusual silicates, as in the
case of the present silver silicate.
Received: February 19. 1979 [Z 217 IE]
German version: Angew. Chem. 91. 500 (1979)
[ l ] F. Liebau in K. H. Wedepohl: Handbook of Geochemistry, Vol. I I / 3 , 14 A 1
Springer-Verlag, Berlin 1972: L. G. Mullinson, J. L. Hutchison, D. A. Jefferson, J. M . Thomas, J. Chem. Soc. Chem. Commun. 1977,910: cf. also Nachr.
Cbem. Tech. Lab. 26, 293 (1978).
[2] M. Jansen, Acta Crystallogr. B 33, 3584 (1977).
131 M. Jansen, Habilitationsschrift, Universitat Giessen 1978.
141 H.-L. Keller. Dissertation. Universitat Giessen 1973.
[ S ] a=1135.6, b=913.1. c=803.8 pm. a=100.32, p=98.62. y=112.83"; 2 = 2 .
2296 observed intensities (diffractometer data); solution by Patterson and
Fourier methods. full matrix LSQ; R=0.049.
Chemical Synthesis of Human Blood Group B
Antigenic Determinant: Type 2 Tetrasaccharide'"'
First Tetrasilicate'"]
By Marfin Jansen and Hans-Lothar Keller[*l
By Marie-Louise Milat and Pierre Sinay"l
On surveying the silicate structures discovered so far, the
absence of a smooth transition from single chains (siO:-) to
The "imidate procedure"['] introduced by our group has
recently ewbled, inter alia, a high-yield synthesis of the trisaccharide
which is considered as the antigenic determinant of the human blood group B in the ABO system. We
[*IDr. habil. M. Jansen
Institut fur Anorganische und Analytische Chemie der Universitat
Heinrich-Buff-Ring 58. D-6300 Lahn-Giessen (Germany)
[*I
Dr. H.-L. Keller
Institut fur Anorganische Chemie der Universitat
Olshausenstrasse 40-60, D-2300 Kiel (Germany)
[**I This work was supported by
464
the Deutsche Forschungsgemeinschaft.
0 Vrrlug Chemie. GmbH, 6940
Werizheim, 1979
[**I
Prof. Dr. P. Sinay. M. L. Milat
Laboratoire de Biochimie Structurale, E.R.A. 739
U.E.R. de Sciences Fondamentales et Appliquees
F-45045 Orleans Cedex (France)
Synthesis of blood-group substances, Part 10.-Part
~ ~ . ~ ? O - O X . ~ ~ / 7 9 / f ~ ~ O $02.50/0
6-V464
9: [2].
Angew. fhem. lnt. Ed. Eiigl. I8 ( 1 9 7 9 ) No. 6
have now succeeded in synthesizing the corresponding terminal tetrasaccharide (10) of type 2.
C H20Bn
o-Gal( 1 - % 3 ) ~ - G a l
/
(1)
b
HO
O
B
n
KHAc
1
a-L-Fuc
-
charide chain (10) of the blood group substance B (type 2) is
finally generated by hydrogenolytic cleavage of (9) with Pd/
C in glacial acetic acid. This tetrasaccharide has been isolated from the alkaline degradation products of a human
blood-group B substancefR1.Physical data of some of the
compounds are listed in Table 1 .
Table I. Physical data of the compounds (2)-(4), (6/, (7). (Y) and ( / O i
155
77
92
i3)
i2)
141
(6)
175
179
91
191
f7)
1/01 [a]
89
90
90
+ 85
+ 76.5
+ 119
+ 36.7
+ 13.6
+ 34
+
14.1
0.9 H,O
1.1 CHCI,
1.2 CHCI,
I .66 CHCI,
I
CHCI,
1.4 CHCI,
0.36 H,O
[a] [uh:l= + 12" (c=0.5,H,O) 181.
A synthesis of the homologous type 1 tetrasaccharide has
recently been reported['].
benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-c~-~-glucopyReceived: February 19, 1979 [ Z 221 IE]
ranoside which, on condensation with 2,3,4,6-tetra-O-acetylGerman version: Angew. Chem. Y 1 . 501 (1979)
a-D-galactopyranosyl bromide (HgBr,, dichloromethane,
molecular sieve 4 A'41) and subsequent deacetylation
(MeONa in methanol), afforded the disaccharide (2). ReacCAS Registry numbers:
tion of (2) with benzaldehyde in the presence of zinc chloride
(2). 70209-54-0;(3).70209-55-1;(4). 70209-56-2;(5), 70267-04-8;(6). 70209-52-3;
gave the benzylidene compound (3), which was then selec(7). 70209-58-4(a), 70267-71-9;(Y), 70209-59-5;(10). 70267-05-9;benzyl 2-acettively ben~oylated[~]
(N-benzoylimidazole in dichloroethane)
amido-3,6-di-O-benzyI-2-deoxy-u-~-glucopyranoside,
55287-49-5:2.3.4.6-tetrato the derivative (4). l-O-[l-(Methylimino)ethyl]-2,3,4-tri-O- 0-acetyl-u-u-galactopyranosyl bromide, 5 12-09-8
As a key starting material we used the readily ac~essible'~]
CHzOBn
,I--0
+
@ ";'"
-
PhCH-OCHz
TsOH
0-C=N-Me
B nO
KHAC
McNO2
O Bn
benzyl-0-L-fucopyranoside(5)16] was condensed @-toluenesulfonic acid/nitromethane) with (4) to provide, after debenzoylation (MeONa in methanol), the protected trisaccharide
(7). The structure of (7) was confirmed by complete deblocking (catalytic hydrogenolysis; Pd/C in pure acetic acid) to
the known['] trisaccharide of type 2. Further proof of the
structure was provided by the NMR spectrum of the benzoate (6).
The expected protected tetrasaccharide (9) was obtained
by reaction of l-O-[l-(methylimino)ethyl]-2,3,4,6-tetra-Obenzyl-f3-D-galactopyranoside @)I2' with (7). The tetrasac-
[I] J:R. Pougny, J.-C. Jucquinet. M . Nassr, D. Ducher, M:L. Milof. P. Sinup. J.
Am. Chem. Soc 99, 6162 (1977).
[2] J:C. Jucquinet, P. Sina~V,Tetrahedron 3.5, 365 (1979).
[3] J.-C. Jucquinet, J.-M. Perir, P. Sinuj, Carbohydr. Res. 38, 305 (1974).
141 J:C. Jucquinet, J:R. Puugn.v, D. Duchet. P. Sinup. 2"" Joint Conference CICACS, Montreal 1977. CARB 44.
[S] G. J. F. Chiftenden, Carbohydr. Res. 16, 495 (1971).
[6]J:C. Jucquinet. P. Sinu~v.J . Chem. Soc. Perkin Trans. I 1'179. 319.
[7] J:C. Jucquinef, P. Sin@, Tetrahedron 32. 1693 (1976).
181 T J. Painter. W M . Wurkins. W. T. J. Morgan, Nature 206. 594 (1965).
Koluf, Angew. Chem. 90. 823 (1978);Angew. Chem. Int. Ed.
(91 H.Puulsen,
Engl. 17. 771 (1978).
c.
CH20Bn
H21Pd
MeN02
___,
___,
CH3COOH
TsOH
191
Angen,. Ckem. Iiit. Ed. Engl. 18 (1979) N o . 6
'
OBn
0 Verlug Ckeinie, GmhH, 6940 Wrinkeim, 197Y
0.5 70-08.33/ 79/0606- 046.5 $ 02.50/0
465
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tetrasaccharide, synthesis, chemical, antigenic, group, determinants, typed, human, blood
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