Oxidation of 2,3,4,6-tetra- O-methyl- d-glucose with alkaline hydrogen peroxide

Abstract

Treatment of 2,3,4,6-tetra- O-methyl- d-glucose with 10 molar equivalents ofn 30% aqueous hydrogen peroxide and 2 molar equivalents of potassium hydroxide afforded, after chromatographic separation, 2,3,4,6-tetra- O-methyl- d-gluconolactone. 1- O-formyl-2,3,5-tri- O-methyl- d-arabinose methyl hemiacetal (7), 2,3,5-tri- O-methyl- d-arabinonolactone, methyl 2,3,5-tri- O-methyl- d-arabinoside, O-(2,4-di- O-methyl- d-erythrose)-(1'→3)-2,4-di- O-methyl- d-erythronic acid, and O-(2,4-di- O-methyl- d-erythrose)-(1′→2)-3- O-methyl- d-glyceraldehyde. The proportions of the products depended on the reaction conditions, especially the time, temperature, and the presence or absence of magnesium hydroxide. Formation of the products is explained by a series of reactions beginning with the addition of hydrogen peroxide to the carbonyl form of the methylated sugar. The adduct, with the help of superoxide radical and a molecule of hydrogen peroxide, breaks up in two ways, giving 2,3,4,6-tetra- O-methyl- d-gluconic acid and 7. The formic ester, on hydrolysis, gives 2,3,5-tri- O-methyl- d-arabinose, which undergoes a similar series of reactions, affording 2,3,5-tri- O-methyl- d-arabinonic acid, and presumably, 1- O-formyl-2,4-di- O-methyl- d-erythrose methyl hemiacetal. Apparently, the latter compound, on hydrolysis, forms a dimer, which, with alkaline hydrogen peroxide, undergoes a similar series of reactions, ultimately affording O-(2,4-di- O-methyl- d-erythrose)-(1→3)-2,4-di- O-methyl- d-erythronic acid and O-(2,4-di- O-methyl- d-erythrose)-(1→2)-3- o-methyl- d-glyceraldehyde. With a larger amount of alkali, under more-severe conditions, oxidation of 2,3,4,6-tetra- O-methyl- d-glucose proceeds further, with production of up to 3 moles of formic acid per mole of methylated sugar.