AbstractIrradiation (∼350 nm) of oxygenated acetonitrile solutions of parathion containing sensitisers such as benzoin and α‐dicarbonyl compounds leads to oxidative desulphurisation at phosphorus, producing paraoxon in reasonable yield. Other degradation reactions also occur, probably as a result of the presence of the 4‐nitrophenyl group in parathion. Under similar irradiation conditions, chlormephos is desulphurised at both the thionate and thiolate moiety. The reactions are rationalised as occurring via peroxy radicals which are generated from the sensitisers. Reaction was not observed when dyes, e.g. rose bengal, were used as sensitisers, which accords with the view that thionates and thiolates are not reactive towards singlet
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