Metabolism of the insecticide metofluthrin in cabbage (Brassica oleracea)

The metabolic fate of metofluthrin [2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (E,Z)-(1R,3R)-2,2-dimethyl-3-(prop-1-enyl)cyclopropanecarboxylate] separately labeled with (14)C at the carbonyl carbon and the α-position of the 4-methoxymethylbenzyl ring was studied in cabbage ( Brassica oleracea ). An acetonitrile solution of (14)C-metofluthrin at 431 g ai ha(-1) was once applied topically to cabbage leaves at head-forming stage, and the plants were grown for up to 14 days. Each isomer of metofluthrin applied onto the leaf surface rapidly volatilized into the air and was scarcely translocated to the untreated portion. On the leaf surface, metofluthrin was primarily degraded through ozonolysis of the propenyl side chain to produce the secondary ozonide, which further decomposed to the corresponding aldehyde and carboxylic acid derivatives. In the leaf tissues, the 1R-trans-Z isomer was mainly metabolized to its dihydrodiol derivative probably via an epoxy intermediate followed by saccharide conjugation in parallel with the ester cleavage, whereas no specific metabolite was dominant for the 1R-trans-E isomer. Isomerization of metofluthrin at the cyclopropyl ring was negligible for both isomers. In this study, the chemical structure of each secondary ozonide derivative was fully elucidated by the various modes of liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance (NMR) spectroscopy together with cochromatography with the synthetic standard, and their cis/trans configuration was examined by the nuclear Overhauser effect (NOE) difference NMR spectrum.