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Updated: Jun 13, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Reactivity of the insecticide fenitrothion toward O and N nucleophiles
Natalia M Rougier1, Raquel V Vico, Rita H de Rossi
1Instituto de Investigaciones en Fisicoquímica de Cordoba (INFIQC), Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Medina Allende y Haya de la Torre, Argentina.
Abstract:
The reactivity of Fenitrothion (1) toward several O- and N-based nucleophiles, including ambident and alpha-nucleophiles, was investigated in basic media at 25 degrees C in water containing 2% 1,4-dioxane. In the reactions with HO(-) and HOO(-) quantitative formation of 3-methyl-4-nitrophenoxide (2) was observed indicating a S(N)2(P) pathway. In the reactions with NH(2)OH, NH(2)O(-), and BuNH(2), demethylfenitrothion (4) was formed along with 2, indicating competition between the S(N)2(P) and S(N)2(C) pathways; no evidence of a S(N)Ar pathway was observed in any case. The observed rate constants were dissected into the values corresponding to the S(N)2(P) and S(N)2(C) pathways. The yield of 4 depends on the nucleophile and on the pH of the reaction, being the main product in the case of BuNH(2). With HOO(-), NH(2)OH, and NH(2)O(-) a significant alpha-effect was observed, confirming the participation of the nucleophile in the rate-limiting step of the reaction.
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