D-glucitol Derivatives Research Articles

Acid-catalysed formation of monoacetals from n-butyraldehyde and certain D-glucitol derivatives

Acid-catalysed condensation of n-butyraldehyde with (a) 1-deoxy-D-glucitol yields a 2,3-acetal as a kinetically controlled product and the 2,4-acetal as the thermodynamically controlled product, (b) 2-deoxy-D-glucitol yields the 1,3-acetal as the kinetically controlled product and the 3,4-acetal(s) as the thermodynamically controlled product, and (c) 3-O-methyl-D-glucitol yields the 2,4-acetal as the predominant product throughout the reaction.In aqueous acid there is no evidence that 1,3-O-butylidene-2-deoxy-D-glucitol undergoes intramolecular conversion; instead substantial hydrolysis to the polyol and aldehyde occurs before the synthesis of the 3,4-acetal(s).

Studies on L-Gulonic Acid Derivatives. II. Benzoyl Migration in Derivatives of D-Glucitol

Benzoyl migrations took place in the partical acid hydrolysis of 1, 2, 3, 5-tetra-O-benzoyl-4, 6-O-ethylidene-D-glucitol (III) to give 1, 2, 4, 6-tetra-O-benzoyl-D-glucitol (IV). This finding is principally based on the experimental result that chromium trioxide oxidation of IV in acetone-sulfuric acid afforded the following five compounds : 1, 3, 5, 6-tetra-O-benzoyl-L-sorbose (V), 1, 2, 4, 6-tetra-O-benzoyl-D-ribo-3-hexulose (IX), 2, 3, 5, 6-tetra-O-benzoyl-L-gulonolactone (VIII), di-O-benzoyl-L-glyceric acid (XI), and benzoylglycolic acid (XII). The formation of VIII from IV in this oxidation indicates that benzoyl migration occurred also during the oxidation.