Probing the simulant behavior of PNPDPP toward parathion and paraoxon: a computational study.

The extreme toxicity of organophosphorus nerve agents and pesticides mandates to employ models or simulants in place of the actual compounds in the laboratory. The importance of simulants is known, however, their efficacy for direct comparison with the toxic organophosphorus compounds is not well documented. We have examined the potential energy surfaces (PES) for the alkaline hydrolysis of pesticides like paraoxon (diethyl 4-nitrophenyl phosphate), parathion (O,O-diethyl O-4-nitrophenyl phosphorothioate) and PNPDPP (4-nitrophenyl diphenyl phosphate), a simulant with MP2/6-311+G*//B3LYP/6-311+G*+ΔG(solv) (HF/6-31+G*) level of theory. The effect of aqueous solvation was considered with the Integral Equation Formalism Polarizable Continuum Model (IEF-PCM). The alkaline hydrolysis of these organophosphorus compounds reveals that the reaction proceeds through the attack of hydroxide ion at the phosphorus center to form a pentacoordinate intermediate. The calculated free energies of activation for the alkaline hydrolysis of paraoxon and parathion are in good agreement with the available experimental activation free energies. The computed results show that the reaction profiles for the alkaline hydrolysis of paraoxon, parathion and PNPDPP are largely similar; however, the rate of hydrolysis of parathion may be higher than that of paraxon and PNPDPP. Such difference arises due to the less electrophilic nature of the phosphorus atom of parathion molecule as observed in the charge analysis study. The conceptual DFT analysis also showed the similar trend for the alkaline hydrolysis of paraoxon, parathion and PNPDPP with hydroxide anion. This computational study provides a quantitative support toward the use of PNPDPP as a simulant for organophosphorus compounds, which cannot be used directly for the laboratory purposes.