The Overoxidation of Carbohydrates with Sodium Metaperiodate

Abstract

The periodate oxidation of 1, 4-anhydroallitol (I), which serves as a model for the periodate oxidation of naturally occurring oligosaccharides, has been examined in the pH range 3-7.5. The overoxidation process which occurs has been shown to require the prior formation of 2, 3-dihydro-6-formyl-3-hydroxy-l, 4-dioxine (IV), which is hydroxylated by periodate to give a product which is further oxidized in a normal fashion. Compound IV has a strong absorption band in the ultraviolet (E278M= 2.49 × 104at pH 8.5) which can be used as an index of the presence of this compound during the oxidation. The structure of IV in solution has been examined by nmr spectroscopy and its rate of formation and oxidation have been shown to be consistent with its being an important intermediate in the overoxidation of I. © 1967, American Chemical Society. All rights reserved.