Electrochemical reduction of substituted pyrimidines in acetonitrile

Abstract

Polarographic studies of several substituted pyrimidines were reinforced by the results from cyclic voltammetry, controlled-potential electrolysis, and spectrophotometric examination of electrolyzed solutions, as well as by the examination of model compounds. Pyrimidines substituted with non-reducible groups (amino, methyl) are reduced in a single, one-electron (1e), diffusion-controlled process, very similar to that for pyrimidine itself. Pyrimidine-4-carboxylic acid exhibits three reduction waves: a very drawn-out acid-reduction wave with unusual properties and, at more negative potential, an adsorption pre-wave and a wave corresponding to the 1e reduction of the pyrimidine moiety. 2-Chloro- and 2-bromopyrimidine each exhibit two polarographic waves; the first, corresponding to irreversible scission of the carbon-halogen bond, has electrochemical properties quite different from those normally expected; the second is due to reduction of the electro-generated pyrimidine. Results are compared with those for the reduction of bromobutane, bromobenzene, and 2-bromopyridine.