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Competitive Reactivity of Tautomers in the Degradation of Organophosphates by Imidazole Derivatives
Author(s) -
Campos Renan B.,
Silva Valmir B.,
Menezes Leociley R. A.,
Ocampos Fernanda M. M.,
Fernandes Juliano M.,
Barison Andersson,
Oliveira Alfredo R. M.,
Tantillo Dean J.,
Orth Elisa S.
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905379
Subject(s) - paraoxon , reactivity (psychology) , chemistry , tautomer , imidazole , catalysis , nucleophile , combinatorial chemistry , degradation (telecommunications) , hydrogen bond , dephosphorylation , organic chemistry , molecule , enzyme , acetylcholinesterase , medicine , telecommunications , pathology , computer science , phosphatase , alternative medicine
The harmful impact caused by pesticides on human health and the environment necessitates the development of efficient degradation processes and control of prohibited stocks of such substances. Organophosphates (OPs) are among the most used agrochemicals in the world and their degradation can proceed through several possible pathways. Investigating the reactivity of OPs with nucleophilic species allows one to propose new and efficient catalyst scaffolds for use in detoxification. In light of the remarkable catalytic activity of imidazole (IMZ) at promoting dephosphorylation processes of OPs, the reactivity of 4(5)‐hydroxymethylimidazole (HMZ) with diethyl‐2,4‐dinitrophenylphosphate (DEDNPP) and Paraoxon are evaluated by combining experimental and theoretical approaches. It is observed that HMZ is an efficient and regiospecific catalyst with reactivity modulated by competing tautomers. To propose an optimal IMZ‐based catalyst, quantum chemical calculations were performed for monosubstituted 4(5)IMZ derivatives that might cleave DEDNPP. Both inductive effects and hydrogen bonding by the substituents are shown to influence barriers and mechanisms.