The decomposition of some organophosphorus insecticides and related compounds in plants

Abstract

To discover the reactions undergone in plants by organophosphorus compounds of the type used as insecticides the non-ionizable metabolites of several compounds were studied. Octamethylpyrophosphoramide (schradan) is degraded in four species of plants. Low yields of heptamethylpyrophosphoramide and a powerful anticholinesterase are obtained besides ionizable compounds. Oxidation of schradan with hydrogen peroxide and with oxygenated liver slices gives the same products in similar proportions. Thus plants probably degrade schradan by oxidation, producing mainly compounds unstable in water, which are hydrolyzed to substituted phosphoric acids. The powerful anticholinesterase is believed to be hydroxymethyl-heptamethylpyrophosphoramide from its chloroform/water partition coefficient and its yield in plants. It may, however, be octamethylpyrophosphoramidic oxide. Turnip plants also degrade the dimethylamide, monomethylamide,n-butylamide,isopropylamide and ethyl ester of tetramethylphosphorodiamidic acid. As these compounds contain no acidic group which can be removed by hydrolysis after oxidation, high yields of compounds extractable from water by chloroform are obtained. None of the parent compounds are hydrolyzed, nor are butyl or wopropyl groups removed in one step. Probably the dimethylamide is demethylated to the monomethylamide in a way similar to schradan. The physical properties of the degradation products of the other compounds indicate that only the dimethylamido groups are attacked, the other groups being inert.OO-diethylO-ethylthioethyl phosphorothionate is converted in plants to at least three compounds extractable by chloroform. Their structures are unknown.OO-diethylS-ethylthioethyl phosphorothiolate is oxidized rapidly in plants toOO-diethylS-ethylsulphinylethyl phosphorothiolate and another compound of unknown structure, both of which are more stable in plants than the parent compound. The same products are formed by the action of hydrogen peroxide on the parent compound. Thus a number of organophosphorus compounds are degraded by oxidation in plants. There is no evidence that their hydrolysis is catalyzed.