Electrochemical reduction of pyrethroid insecticides based on esters of α-cyano-3-phenoxybenzyl alcohol at glassy carbon and mercury electrodes in acetonitrile

Abstract

Abstract The electrochemical reduction of eight commercially important pyrethroid insecticides which are esters of either α-cyano-3-phenoxybenzyl alcohol (cycloprothrin, cyphenothrin, cyhalothrin, deltamethrin, esfenvalerate and cypermethrin) or 4-fluro-α-cyano-3-phenoxybenzyl alcohol (cyfluthrin and flumethrin) has been studied under conditions of voltammetry and bulk electrolysis at both glassy carbon and mercury electrodes in acetonitrile. In general, the peak potential of the initial reduction process observed at very negative potentials at both electrode surfaces shifts to a more positive value under conditions of consecutive potential cycling. At the hanging mercury drop electrode the reduction occurs at even more negative potentials than at a glassy carbon electrode because a blocking mechanism appears to be operative. Despite this major difference in the primary reduction step, common voltammetric features are observed at less negative potentials on second and subsequent cycles of the electrode potential at either electrode surface. For example, the initial reduction process always results in the formation of a species which is reversibly reduced at less negative applied potentials. Furthermore, despite the definition of the voltammetric response being highly sensitive to the individual pyrethroid structure, long time-scale bulk electrolysis experiments at glassy carbon or mercury pool electrodes led to the formation of analogous final products. The fact that pyrethroids with a widely varying range of acid moieties exhibit similar voltammetric behaviour suggests that the acid moiety is not directly involved in the initial electron transfer process. Controlled potential electrolysis studies at both electrode surfaces coupled with HPLC and mass spectral identification of products obtained after ethylation with ethyl iodide showed that the reduction mechanism on the longer time-scale involves cleavage of the ester with liberation of free cyanide ion. The major reduction product identified was the anion of either 3-phenoxybenzoic acid or 4-fluoro-3-phenoxybenzoic acid in yields ranging from 31 to 66%.