A Carbon-13 Nuclear Magnetic Resonance Study of Chlorinated and Polyol Analogs of Glucose and Related Oligomers

Abstract

Complete assignments of the carbon-13 n.m.r. spectra of the following compounds in aqueous solution are presented: 6-chloro-6-deoxy-D-glucose, 6-O-methyl-D-glucose, ribitol, glucitol, 4-O-methyl-glucitol, maltose, maltitol, 6,6′-dichloro-6,6′-dideoxymaltose, 6′-chloro-6′-deoxy-maltose, isomaltose, isomaltitol, and 6′-chloro-6′-deoxyisomaltose. Some earlier assignments for maltose are reversed. Chlorination on the exocyclic carbon of the glucopyranose ring usually results in a substantial decrease in the chemical shift of the substituted carbon (−17 p.p.m.) and the next-nearest carbon (−1.2 p.p.m.); methylation leads to an increased chemical shift for the contiguous carbon (+10 p.p.m.) and only small changes for other carbons in the molecule. The response to 4-O-methylation in glucitol is opposite for C-3 (+0.7 p.p.m.) and C-5 (−0.8 p.p.m.) demonstrating that response of a particular carbon to substitution at a neighboring carbon depends upon the configuration of the particular carbon. Dissolution of these compounds in pyridine results in a bunching together of resonances which makes unambiguous assignments very difficult. The data for this series of compounds are useful in assigning the more complex spectra of microbial polysaccharides.