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Preparation of 6-O-Acyl Amylose Derivatives

Published online by Cambridge University Press:  15 February 2011

A. L. Cimecioglu ,
D. H. Ball ,
D. L. Kaplan  and
S. H. Huang
A. L. Cimecioglu
Affiliation:
U.S. Army Natick RD&E Center, Biotechnology Division, Natick MA 01760 University of Connecticut, Biodegradable Polymer Research Consortium, Institute of Materials Science, Storrs, CT 06269
D. H. Ball
Affiliation:
U.S. Army Natick RD&E Center, Biotechnology Division, Natick MA 01760
D. L. Kaplan
Affiliation:
U.S. Army Natick RD&E Center, Biotechnology Division, Natick MA 01760
S. H. Huang
Affiliation:
University of Connecticut, Biodegradable Polymer Research Consortium, Institute of Materials Science, Storrs, CT 06269
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Abstract

Two new direct approaches for selective 6-O-acylation of amylose under homogeneous conditions were investigated. In the first method, amylose was initially brominated at C-6 using Nbromosuccinimide and triphenylphosphine in N,N-dimethyfformamide containing lithium bromide. The procedure was found to be highly selective and proceeded with no detectable reaction at the secondary positions. Several 6-bromo-6-deoxyamylose derivatives were prepared with different degrees of substitution by changing the molar equivalence of the reactants. In the second stage these were converted into 6-laurate esters by treatment with cesium laurate in dimethylsulfoxide, which proceeded rapidly under mild conditions. In the second method, the feasibility of 6-O-benzoylation in one step using the Mitsunobu reaction was evaluated. Amylose was treated with diethylazodicarboxylate in the presence of triphenylphosphine and benzoic acid in dimethysulfoxide under ambient conditions. While exclusively 6-O-benzoylation resulted up to degree of substitutions of ca. 0.5, at higher values a small amount of esterification at secondary hydroxyl groups also occurred. Products were characterized by 13C NMR, FTIR and elemental analyses.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 330: Symposium S – Biomolecular Materials by Design , 1993 , 7
Copyright
Copyright © Materials Research Society 1994

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References

REFERENCES

1. Yalpani, M., “Polysaccharidesu”, Elsevier, Amsterdam 1988 Google Scholar
2. Yalpani, M., Tetrahedron, 41, 2957 (1985)Google Scholar
3. Beck, R. H. F., Fitton, M. G., and Kricheldorf, H. R., in ‘Handbook of Polymer Synthesis”, Kricheldorf, H. R. (ed.), Part B, Marcel Dekker, New York 1992.Google Scholar
4. Horton, D., in ‘New Developments in Industrial Polysaccharides”,Crescenzi, V., Dea, I. C. M., and Stivala, S. S. (eds.), Gordon Breach, New York, p.173, 1985.Google Scholar
5. Vigo, T. L., Daigle, D. J., and Welch, C. M., J. Polym. Sci. Polym. Lett. Ed., 10, 397 (1972)CrossRefGoogle Scholar
6. Ishii, T., Ishizu, A., and Nakano, J., Carbohydr. Res., 59, 155 (1977)Google Scholar
7. McCormick, C. L., and Callais, P., Polymer, 28, 2317 (1987)Google Scholar
8. McCormick, C. L., Dawsey, T. R., and Newman, J. K., Carbohydr. Res., 208,183 (1990)Google Scholar
9. Takeo, K., Sumimoto, T., and Kuge, T., Starke, 26, 111 (1974)CrossRefGoogle Scholar
10. Ball, D. H., Wiley, B. J., and Reese, E. T., Can. J. Microbiol., 38, 324 (1992)Google Scholar
11. Ball, D. H., Reese, E. T., and Stenhouse, P. J., in “Bioderadable Polymers and Packaging”, Ching, C., Kaplan, D. L., and Thomas, E.(eds.), Technomic, Lancaster, PA 1993, p111.Google Scholar
12 Horton, D. and Lehman, J., Carbohydr. Res., 61, 553 (1978)Google Scholar
13. Mitsunobu, O., Synthesis, 1 (1981), and the references thereinGoogle Scholar
14. Hanessian, S., Ponpipom, M. M., and Lavalle, P., Carbohydr. Res., 24, 45 (1972)Google Scholar
15. Hodosi, G., Podanyi, B., and Kuszmann, J., Carbohydr. Res., 230, 327 (1992)Google Scholar
16. Boger, J., Corcoran, R. J., and Lehn, J-M., Helv. Chim. Acta., 61, 2190 (1978)Google Scholar
17. Pfeffer, P. E., and Silbert, L., J. Org. Chem., 41, 1373 (1976)Google Scholar
18. Wang, S-S., Gisin, B. F., Winter, D. P., Makofske, R., Kulesha, I. D., Tzougraki, C., and Meinhofer, J., J. Org. Chem., 42,1286 (1977)Google Scholar
19. Cimecioglu, A. L. and East, G. C., J. Polym. Sci. Polym. Chem., 30, 313 (1992)Google Scholar