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Theoretical investigation of the neutral hydrolysis of diethyl 4-nitrophenyl phosphate (paraoxon) in aqueous solution

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Abstract

In this work the neutral or spontaneous hydrolysis of paraoxon, one of the most popular organophosphate pesticides, in aqueous solution was investigated at the DFT and MP2 levels of theory, using a combination of local solvation of the phosphoryl group with explicit water molecules, and treating the long range solvent effects using continuum solvation model. In contrast to the alkaline hydrolysis, the neutral hydrolysis takes place in two steps, through an AN + DN mechanism, with formation of a pentacoordinate phosphorane intermediate. The reaction has activation free energies of 31.8 and 1.9 kcal mol−1 for the first and second steps, respectively, and has an overall reaction free energy of −9.3 kcal mol−1, computed at the MP2/6–311++G(2d,2p)//B3LYP/6–31+G(d) level of theory. The reaction proceeds through a sequence of proton transfer processes from the attacking water molecule and ends with the protonation of the nitrophenolate leaving group. Explicit description of the local solvating water molecules is essential to describe the proton transfer processes along the reaction coordinate and to stabilize the pentacoordinate intermediate formed. The neutral hydrolysis is very slow and has an overall rate constant of 3.05 × 10−11 s−1, computed at the MP2/6–311++G(2d,2p)//B3LYP/6–31+G(d) level of theory. This result, in conjunction with the sensitivity of the rate constant to the experimental conditions, indicates that the hydrolysis of paraoxon in aqueous solution can be even slower than predicted experimentally.

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Acknowledgments

The authors would like to thank the CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico, INCT-Catálise) and FAPEMIG (Fundação de Amparo à Pesquisa do Estado de Minas Gerais) for the financial support and research grants.

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Authors and Affiliations

  1. eCsMoLab: Laboratório de Estudos Computacionais em Sistemas Moleculares, Departamento de Química, ICEx, Universidade Federal de Minas Gerais, 31270-901, Pampulha, Belo Horizonte, MG, Brazil

    Marcelo A. Chagas, Eufrásia S. Pereira, Júlio Cosme S. Da Silva & Willian R. Rocha

  2. GQC: Grupo de Química Computacional, Instituto de Química e Biotecnologia, IQB, Universidade Federal de Alagoas, Campus A. C. Simões, Maceió, AL, 57072-900, Brazil

    Júlio Cosme S. Da Silva

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  1. Marcelo A. Chagas
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  2. Eufrásia S. Pereira
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  3. Júlio Cosme S. Da Silva
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  4. Willian R. Rocha
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Correspondence to Willian R. Rocha.

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This paper belongs to Topical Collection XIX - Brazilian Symposium of Theoretical Chemistry (SBQT2017)

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Chagas, M.A., Pereira, E.S., Da Silva, J.C.S. et al. Theoretical investigation of the neutral hydrolysis of diethyl 4-nitrophenyl phosphate (paraoxon) in aqueous solution. J Mol Model 24, 259 (2018). https://doi.org/10.1007/s00894-018-3798-1

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