Artículo de revista
Specific nucleophile-electrophile interactions in nucleophilic aromatic substitutions
Fecha
2013Registro en:
Organic and Biomolecular Chemistry, Volumen 11, Issue 14, 2018, Pages 2302-2309
14770520
10.1039/c3ob27450k
Autor
Ormazábal Toledo, Rodrigo
Contreras Ramos, Renato
Tapia, Ricardo A.
Campodónico, Paola R.
Institución
Resumen
We herein report results obtained from an integrated experimental and theoretical study on aromatic nucleophilic substitution (SNAr) reactions of a series of amines towards 1-fluoro-2,4-dinitrobenzene in water. Specific nucleophile-electrophile interactions in the title reactions have been kinetically evaluated. The whole series undergoes SNAr reactions where the formation of the Meisenheimer complex is rate determining. Theoretical studies concerning specific interactions are discussed in detail. It is found that H-bonding effects along the intrinsic reaction coordinate profile promote the activation of both the electrophile and the nucleophile. Using these results, it is possible to establish a hierarchy of reactivity that is in agreement with the experimental data. Second order energy perturbation energy analysis highlights the strong interaction between the ortho-nitro group and the acidic hydrogen atom of the amine. The present study strongly suggests that any theoretical analysis