Sodium hypochlorite as a selective oxidant for organic compounds

Abstract

A study of the reactions of sodium hypochlorite with a wide variety of compounds has been carried out. The data indicate that a structure capable of producing a carbanion stable enough to undergo halogenation is oxidized by sodium hypochlorite to a ketone or a carboxylic acid. How far the oxidation will proceed is determined by enolateion resonance stabilization and by inductive and steric effects of the activating group (e.g.CO, –NO₂, –CN, or –CO₂H). Unactivated aromatic, hydroaromatic, alicyclic, and alkane systems are not oxidized. Heteroaromatic ring systems capable of undergoing azomethine-type addition can readily be cleaved, whereas benzenoid ring systems undergo no change. Oxidation of an activated alicyclic compound containing a tertiary sp³ carbon system may result in loss of one, two, or three carbon atoms as CO₂ or CHCl₃via 1,3- and 1,4-halogenation steps. Based on this investigation, a new methodology of oxidation has been developed for structural elucidation of complex materials such as coal.