Thio-Induced Organophosphate Breakdown Promoted by Methimazole: an Experimental and Theoretical Study.

Autor: Campos RB; Departamento Acadêmico de Química e Biologia, Universidade Tecnológica Federal do Paraná, Rua Deputado Heitor de Alencar Furtado, 5000, 81280-340, Curitiba, Brazil., Capato LA; Departamento Acadêmico de Química e Biologia, Universidade Tecnológica Federal do Paraná, Rua Deputado Heitor de Alencar Furtado, 5000, 81280-340, Curitiba, Brazil., Soares PM; Chemistry Departament, Universidade Federal do Paraná (UFPR), CP 19081, CEP 81531-990, Curitiba, PR, Brazil., Tantillo DJ; Department of Chemistry, University of California-Davis, Davis, California, 95616, United States., Orth ES; Chemistry Departament, Universidade Federal do Paraná (UFPR), CP 19081, CEP 81531-990, Curitiba, PR, Brazil.
Jazyk: angličtina
Zdroj: ChemPlusChem [Chempluschem] 2024 Jun; Vol. 89 (6), pp. e202300756. Date of Electronic Publication: 2024 Mar 14.
DOI: 10.1002/cplu.202300756
Abstrakt: Investigating the reactivity of small nucleophilic scaffolds is a strategic approach for the design of new catalysts aiming at effective detoxification processes of organophosphorus compounds. The drug methimazole (MMZ) is an interesting candidate featuring two non-equivalent nucleophilic centers. Herein, phosphoryl transfer reactions mediated by MMZ were assessed by means of spectrophotometric kinetic studies, mass spectrometry (MS) analyses, and density functional theory (DFT) calculations using the multi-electrophilic compound O,O-diethyl 2,4-dinitrophenyl phosphate (DEDNPP). MMZ anion acts primarily as an S-nucleophile, exhibiting a nucleophilic activity comparable to that of certain oximes featuring alpha-effect. Selective nucleophilic aromatic substitution was observed, consistent with the DFT prediction of a low energy barrier. Overall, the results bring important advances regarding the mechanistic understanding of nucleophilic dephosphorylation reactions, which comprises a strategic tool for neutralizing toxic organophosphates, hence promoting chemical security.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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