Conclusions
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1.
(2)3-Azido-(2)3-desoxy-6-O-tritylpolysaccharide was synthesized by replacing the tosyloxy groups by azide groups in 2(3)-O-tosyl-6-O-triacetylcellulose in hexamethylphosphoric triamide medium, the reduction of which with aluminum lithium hydride gave a (2)3-amino-(2)3-desoxypolysaccharide with a degree of substitution of 0.5–0.7 in amino groups.
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2.
The tosylation of 6-O-tritylcellulose goes predominantly at C-2. When the degree of substitution of tosyloxy groups is 0.7 the degree of substitution of tosyloxy groups at C-2 is equal to 0.6, and 0.1 at C-3.
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3.
The replacement of tosyloxy groups by azide groups in the 2-O-tosyl-6-O-tritylglucose units of 2(3)-O-tosyl-6-O-tritylcellulose goes predominantly via the formation of 2,3-anhydro rings, the opening of which by the azide anion proceeds mainly via attack at C-3. The reaction proceeds to a lesser degree via the direct replacement of the tosyloxy groups by the azide anion, with an inversion of the configuration at C-2. In contrast, the insertion of azide groups into the 3-O-tosyl-6-O-tritylglucose units proceeds mainly by direct substitution.
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Literature cited
A. I. Usov, N. I. Nosova, S. I. Firgang, and O. P. Golova, Vysokomolekul. Soedin.,15A, 1150 (1973).
W. M. Hearon, G. D. Hiatt, and C. R. Fordyce, J. Am. Chem. Soc.,65, 2449 (1943).
J. Honeyman, J. Chem. Soc., 168 (1947).
G. N. Smirnova, A. I. Polyakov, and Z. A. Rogovin, Vysokomolekul. Soedin.,7, 972 (1965).
R. D. Guthrie and D. Murphy, J. Chem. Soc., 5288 (1963).
F. D. Cramer, H. Otterbach, and H. Springman, Chem. Ber.,92, 384 (1953).
J. Jary, Z. Kefurtova, and J. Kovar, Collect. Czechoslov. Chem. Commun.,34, 1452 (1969).
L. F. Wiggins, J. Chem. Soc., 18 (1947).
R. L. Whistler and L. W. Doner, J. Org. Chem.,35, 3562 (1970).
U. G. Noyak and R. L. Whistler, J. Org. Chem.,34, 3819 (1969).
R. V. Lemieux and P. Chu, J. Am. Chem. Soc.,80, 4745 (1958).
S. Roseman and J. Ludowieg, J. Am. Chem. Soc.,76, 301 (1954).
A. B. Foster, M. Stacey, and S. V. Vardheim, Acta Chem. Scand.,12, 1605 (1958).
P. A. Levene and G. M. Meyers, J. Biol. Chem.,55, 221 (1923).
R. Kuhn, W. Bister, and H. Fischer, Ann. Chem.,617, 109 (1958).
H. H. Baer, J. Am. Chem. Soc.,84, 83 (1962).
B. Coxon and L. Hough, J. Chem. Soc., 1463 (1961).
B. Coxon and L. Hough, J. Chem. Soc., 1643 (1961).
Y. Ali and A. C. Richardson, Carbohyd. Res.,5, 441 (1967).
A. Gotshalka (editor), Glycoproteins (Russian translation], Vol. 1, Mir (1969), p. 200.
S. Peat and L. F. Wiggins, J. Chem. Soc., 1810 (1938).
I. Jezo, Chem. Zvesti,27, 381 (1973).
R. D. Guthrie, A. M. Prior, and S. E. Creasey, J. Chem. Soc., C 1961 (1970).
N. A. Hughes and P. R. H. Speakman, J. Chem. Soc., 2236 (1965).
T. S. Gardner and C. B. Purves, J. Am. Chem. Soc.,64, 1539 (1942).
F. G. Fischer and N. J. Nebel, Z. Physik. Chem.,302, 10 (1955).
L. S. Bolotnikova, S. N. Danilov, and T. I. Samsonova, Zh. Prikl. Khim.,39, 176 (1966).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2575–2581, November, 1974.
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Usov, A.I., Nosova, N.I., Firgang, S.I. et al. Synthesis of azido derivative from 2(3)-O-tosyl-6-O-tritylcellulose and its conversion to an a minopolysacchride. Russ Chem Bull 23, 2481–2487 (1974). https://doi.org/10.1007/BF00922136
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DOI: https://doi.org/10.1007/BF00922136