Oxidation of Methylmalonic Acid by Cerium(IV). Evidence for Parallel Reaction Pathways

Abstract

The reaction between methylmalonic acid (MeMA) and Ce(IV) ion in 1 M sulfuric acid/D 2 SO 4 has been studied by means of 1 H- and 13 C-NMR. When MeMA is in excess, acetic acid, hydroxymethylmalonic acid, and pyruvic acid are formed as stable end products. When Ce(IV) is in stoichiometric excess, acetic acid is the only product. Approximately 70−80% of the MeMA forms rapidly acetic acid with hydroxymethylmalonic acid and pyruvic acid as reactive intermediates. The remaining MeMA reacts along parallel pathways and forms two intermediates, which slowly convert to hydroxymethylmalonic acid and pyruvic acid, respectively.