Electro-organic reactions. Part II. Mechanism of the kolbe electrolysis of substituted phenylacetate ions

For the anodic oxidation of phenylacetate and substituted phenylacetate ions changes in the distribution of products have been related to changes in electrochemical parameters, nuclear substitution, and the concentration of added perchlorate ions. The results support a reaction mechanism which involves the important adsorption of carboxylate perchlorate ions and according to which added anions and bulky substituents cause surface effects which significantly effect the competition between radical and carbenium ion pathways. For p-methoxyphenylacetate ions oxidation is probably initiated by electron transfer from the aromatic nucleus (pseudo-Kolbe reaction). From a steady state kinetic analysis expressions have been derived which relate product distribution with structural, electrochemical, and adsorption parameters.