Mechanistic investigation of oxidation of 6-deoxyhexoses by sodium <i>N</i>-chloro-<i>p</i>-toluenesulfonamide in alkaline medium

Abstract

The kinetics and mechanism of oxidation of L-fucose and L-rhamnose by chloramine-T (CAT) in alkaline medium has been investigated at 40°C. The rate of the reaction is first order with respect to [sugar][CAT] and [hydroxide ion]. The reaction rate is influenced by a change in ionic strength of the medium and the dielectric effect has been found to be

negative. Proton inventory studies have been made in H₂O- D₂O mixtures. Activation parameters have been determined from the Arrhenius plots. HPLC and GLC-MS analyses of the products indicate that 6-deoxyhexoses are oxidized to a mixture of aldonic acids. The proposed mechanism is consistent with the observed results.