Reactive intermediates in pesticide metabolism: Peracid oxidations as possible biomimetic models

Abstract

1. Reactive intermediates generated by metabolic epoxidation, N-oxidation and S-oxidation are often identical to those obtained on peracid oxidation as illustrated by studies with a variety of pesticides.

2. Epoxidation reactions carried out metabolically or with peracids lead to transitory or unstable epoxychrysanthemic acid, epoxycyclopentenolone and epoxyfuran derivatives from pyrethroids, and geranyl-derived diepoxides and epoxydiols from juvenoids.

3. N-Oxidation with microsomal oxidases or peracids activates hydroxylamine ether proinsecticides and dimethylphosphoramide and aminodiphenyl ether promutagens, but the peracid system is not always a suitable biomimetic model.

4. Sulphoxidations with peracids appear to give the same reactive intermediates as those involved in metabolism of S-alkyl thiocarbamate and S-methyl-triazinone herbicides, S-chloroallyl promugatens, and S-propyl phosphorothiolate and phosphinyl-iminodithiolane proinsecticides.