Isolation of 2-fluorocitrate produced by in vivo dealkylation of 29-fluorostigmasterol in an insect.
A novel pro-insecticide, 29-fluorostigmasterol, is proposed to cause mortality due to release of fluoroacetate during side chain dealkylation. The 29-3H-labeled substrate was fed to third instar tobacco hornworms (Manduca sexta) and erythro-2-fluoro-[2-3H] citrate was isolated in 0.012% yield by ion-exchange, silica gel, and reverse-phase chromatography of the tricarboxylic acid, trimethyl ester, and trimethyl ester benzoate, respectively. The less toxic 29-fluoro-[29-3H]sitosterol did not provide sufficient labeled fluorocitrate to allow isolation, while a more toxic 16-3H-labeled 16-fluorofatty acid gave nearly 1% conversion to labeled fluorocitrate. This is the first direct chemical evidence for the fate of the two carbons removed during phytosterol dealkylation in an insect. It is also the first use of labeled fluoroacetate precursors to identify labeled 2-fluorocitrate as an in vivo metabolite of these precursors.
D002851:Chromatography, High Pressure Liquid; D002951:Citrates / Q000096:biosynthesis / Q000302:isolation & purification*; D007814:Larva / Q000378:metabolism; D007915:Lepidoptera / Q000378:metabolism*; D009682:Magnetic Resonance Spectroscopy; D009036:Moths / Q000378:metabolism*; D010840:Phytosterols / Q000378:metabolism*; D013265:Stigmasterol / Q000031:analogs & derivatives / Q000378:metabolism*; D014316:Tritium
D002951:Citrates; D010840:Phytosterols; D014316:Tritium; C007744:fluorocitrate; C042478:29-fluorostigmasterol; D013265:Stigmasterol