2015 |
Alarcon-Esposito, J; Tapia, R A; Contreras, R; Campodonico, P R Changes in the Snar Reaction Mechanism Brought About by Preferential Solvation Artículo de revista Rsc Advances, 5 (120), pp. 99322-99328, 2015, ISSN: 2046-2069. Resumen | Enlaces | BibTeX | Etiquetas: aminolysis, benzenesulfonates, binary ionic liquids, mixtures, molecules, nucleophilic-substitution pathways reactions, regioselectivity, secondary-amines, solvent @article{RN273, title = {Changes in the Snar Reaction Mechanism Brought About by Preferential Solvation}, author = { J. Alarcon-Esposito and R.A. Tapia and R. Contreras and P.R. Campodonico}, url = {/brokenurl#<Go to ISI>://WOS:000365328000069}, doi = {10.1039/c5ra20779g}, issn = {2046-2069}, year = {2015}, date = {2015-01-01}, journal = {Rsc Advances}, volume = {5}, number = {120}, pages = {99322-99328}, abstract = {We herein report an experimental and theoretical study on preferential solvation effects for the reactions of 1-fluoro and 1-chloro-2,4-dinitrobenzene towards morpholine in acetonitrile, water and mixtures of them of varying compositions. A detailed kinetic study opens the possibility of analyzing preferential solvation and reaction rates. The kinetic study was complemented with an exploration of the potential energy surface in order to analyze the nature of the molecular interactions. For the fluorine derivative, this analysis reveals that the solvation of the TS in the mode TS1F-water/MeCN clearly outweighs the solvation of TS1F-MeCN/water, thereby suggesting that there is preferential solvation in favor of the aqueous phase.}, keywords = {aminolysis, benzenesulfonates, binary ionic liquids, mixtures, molecules, nucleophilic-substitution pathways reactions, regioselectivity, secondary-amines, solvent}, pubstate = {published}, tppubtype = {article} } We herein report an experimental and theoretical study on preferential solvation effects for the reactions of 1-fluoro and 1-chloro-2,4-dinitrobenzene towards morpholine in acetonitrile, water and mixtures of them of varying compositions. A detailed kinetic study opens the possibility of analyzing preferential solvation and reaction rates. The kinetic study was complemented with an exploration of the potential energy surface in order to analyze the nature of the molecular interactions. For the fluorine derivative, this analysis reveals that the solvation of the TS in the mode TS1F-water/MeCN clearly outweighs the solvation of TS1F-MeCN/water, thereby suggesting that there is preferential solvation in favor of the aqueous phase. |
2014 |
Gazitua, M; Tapia, R A; Contreras, R; Campodonico, P R Mechanistic Pathways of Aromatic Nucleophilic Substitution in Conventional Solvents and Ionic Liquids Artículo de revista New Journal of Chemistry, 38 (6), pp. 2611-2618, 2014, ISSN: 1144-0546. Resumen | Enlaces | BibTeX | Etiquetas: aminolysis aryl azides, benzenesulfonates, kinetics, rationalization, regioselectivity, secondary-amines, solvation @article{RN224, title = {Mechanistic Pathways of Aromatic Nucleophilic Substitution in Conventional Solvents and Ionic Liquids}, author = { M. Gazitua and R.A. Tapia and R. Contreras and P.R. Campodonico}, url = {/brokenurl#<Go to ISI>://WOS:000336821000059}, doi = {10.1039/c4nj00130c}, issn = {1144-0546}, year = {2014}, date = {2014-01-01}, journal = {New Journal of Chemistry}, volume = {38}, number = {6}, pages = {2611-2618}, abstract = {Solvation effects on the reaction mechanism of the title reactions have been kinetically evaluated in 21 conventional solvents and 17 ionic liquids. Solvent polarity affects the catalyzed and non-catalyzed SNAr pathways differently. The ambiphilic character of water and formamide, which act as a hydrogen bond donor/acceptor, induces nucleophilic activation at the nitrogen center of the nucleophile. The ionic liquid EMIMDCN appears to be the best solvent for the SNAr route probably due to the high polarizability of the dicyanamide anion.}, keywords = {aminolysis aryl azides, benzenesulfonates, kinetics, rationalization, regioselectivity, secondary-amines, solvation}, pubstate = {published}, tppubtype = {article} } Solvation effects on the reaction mechanism of the title reactions have been kinetically evaluated in 21 conventional solvents and 17 ionic liquids. Solvent polarity affects the catalyzed and non-catalyzed SNAr pathways differently. The ambiphilic character of water and formamide, which act as a hydrogen bond donor/acceptor, induces nucleophilic activation at the nitrogen center of the nucleophile. The ionic liquid EMIMDCN appears to be the best solvent for the SNAr route probably due to the high polarizability of the dicyanamide anion. |
2015 |
Changes in the Snar Reaction Mechanism Brought About by Preferential Solvation Artículo de revista Rsc Advances, 5 (120), pp. 99322-99328, 2015, ISSN: 2046-2069. |
2014 |
Mechanistic Pathways of Aromatic Nucleophilic Substitution in Conventional Solvents and Ionic Liquids Artículo de revista New Journal of Chemistry, 38 (6), pp. 2611-2618, 2014, ISSN: 1144-0546. |