Mechanism for the S N Ar reaction of atrazine with endogenous thiols: experimental and theoretical study

The reaction mechanism in aromatic nucleophilic substitution reactions is discussed using kinetic study complemented with quantum chemical calculations. The model system is the reaction of a series of biothiols toward atrazine (ATZ) in aqueous media. The proposed reaction mechanism discloses a non-c...

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Bibliographic Details
Published in:New journal of chemistry 2017, Vol.41 (21), p.12671-12677
Main Authors: Calfumán, K., Gallardo-Fuentes, S., Contreras, R., Tapia, R. A., Campodónico, P. R.
Format: Article
Language:English
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Summary:The reaction mechanism in aromatic nucleophilic substitution reactions is discussed using kinetic study complemented with quantum chemical calculations. The model system is the reaction of a series of biothiols toward atrazine (ATZ) in aqueous media. The proposed reaction mechanism discloses a non-catalyzed pathway and the presence of a deprotonated (thiolate) nucleophile in water suggests that the reaction mechanism is borderline between a stepwise route and a concerted process. The full analysis of the potential energy surface reinforces the addition/elimination mechanism. Despite numerous attempts to locate transition structures associated with the leaving group departure, they were unsuccessful, presumably because this step is extremely fast.
ISSN:1144-0546
1369-9261
DOI:10.1039/C7NJ02708G