Acceleration of nucleophilic attack on an organophosphorothioate neurotoxin, fenitrothion, by reactive counterion cationic micelles. Regioselectivity as a probe of substrate orientation within the micelle.

31P NMR and UV-vis spectrometric evidence has revealed an unexpected regioselectivity in the reaction of fenitrothion, 1, an organophosphorus pesticide, with the cetyltrimethylammonium (CTA) surfactants CTAOH and CTAMINA, that incorporate the reactive counterions OH- and MINA- (the anti-pyruvaldehyde 1-oximate anion). While both micellar solutions accelerate decomposition of 1 compared to aqueous OH- alone, CTAMINA produced the largest rate enhancement (ca. 10(5)) at a pH (8.39) appropriate for environmental applications. In the absence of surfactant, reaction proceeds solely via the SN2(P) pathway. In the presence of surfactant but below the critical micelle concentration (cmc), a competitive SN2(C) pathway was observed in addition to SN2(P). Above the cmc, however, the CTAOH reaction again proceeded solely via the SN2(P) pathway while both pathways were operative with CTAMINA. The changes in reactivity and mechanistic pathway are discussed in terms of premicellar and micellar influences on rates and regioselectivity. A proposal that would account for the observed regioselectivity in the micellar system is that the aromatic ring and aliphatic side-chains of 1 are oriented toward the micellar interior, while the P=S moiety faces the aqueous pseudophase.