Mechanism for the SNAr reaction of atrazine with endogenous thiols: experimental and theoretical study. (2nd October 2017)

• Record Type: Journal Article
• Authors: Calfumán, K.; Gallardo-Fuentes, S.; Contreras, R.; Tapia, R. A.; Campodónico, P. R.
• Is Part Of: New journal of chemistry. Volume 41:Number 21(2017)
• Page Start: 12671
• Page End: 12677
• Publication Date: 2017-10-02
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c7nj02708g
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : The mechanism for the SN Ar reaction of atrazine with endogenous thiols: a stepwise or concerted process? Abstract : 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.