Fipronil insecticide: novel photochemical desulfinylation with retention of neurotoxicity.
Fipronil is an outstanding new insecticide for crop protection with good selectivity between insects and mammals. The insecticidal action involves blocking the lambda-aminobutyric acid-gated chloride channel with much greater sensitivity of this target in insects than in mammals. Fipronil contains a trifluoromethylsulfinyl moiety that is unique among the agrochemicals and therefore presumably important in its outstanding performance. We find that this substituent unexpectedly undergoes a novel and facile photoextrusion reaction on plants upon exposure to sunlight, yielding the corresponding trifluoromethylpyrazole, i.e., the desulfinyl derivative. The persistence of this photoproduct and its high neuroactivity, resulting from blocking the lambda-aminobutyric acid-gated chloride channel, suggest that it may be a significant contributor to the effectiveness of fipronil. In addition, desulfinylfipronil is not a metabolite in mammals, so the safety evaluations must take into account not only the parent compound but also this completely new environmental product.
Department of Environmental Science, Policy, and Management, University of California, Berkeley 94720-3112, USA.
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D000818:Animals; D001921:Brain / Q000378:metabolism; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000378:metabolism; D018118:Chloride Channels / Q000378:metabolism; D018360:Crystallography, X-Ray; D004791:Enzyme Inhibitors / Q000378:metabolism; D005260:Female; D008401:Gas Chromatography-Mass Spectrometry; D006793:Houseflies; D007306:Insecticides / Q000737:chemistry* / Q000378:metabolism / Q000633:toxicity*; D015640:Ion Channel Gating; D007928:Lethal Dose 50; D009682:Magnetic Resonance Spectroscopy; D008297:Male; D051379:Mice; D008968:Molecular Conformation; D009498:Neurotoxins / Q000737:chemistry* / Q000378:metabolism / Q000633:toxicity*; D010777:Photochemistry; D011720:Pyrazoles / Q000737:chemistry* / Q000378:metabolism / Q000633:toxicity*; D005680:gamma-Aminobutyric Acid / Q000378:metabolism
D019086:Bridged Bicyclo Compounds, Heterocyclic; D018118:Chloride Channels; D004791:Enzyme Inhibitors; D007306:Insecticides; D009498:Neurotoxins; D011720:Pyrazoles; C091518:1-(4-ethynylphenyl)-4-propyl-2,6,7-trioxabicyclo(2.2.2)octane; D005680:gamma-Aminobutyric Acid; C082360:fipronil