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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

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