2018 |
Gazitua, M; Tapia, R A; Contreras, R; Campodonico, P R Effect of the Nature of the Nucleophile and Solvent on an Snar Reaction Artículo de revista New Journal of Chemistry, 42 (1), pp. 260-264, 2018, ISSN: 1144-0546. Resumen | Enlaces | BibTeX | Etiquetas: amines, aromatic aryl azides, conventional ionic kinetics, liquids, preferential reaction-mechanism, regioselectivity solvation, solvents, substitutions, temperature @article{RN422, title = {Effect of the Nature of the Nucleophile and Solvent on an Snar Reaction}, author = { M. Gazitua and R.A. Tapia and R. Contreras and P.R. Campodonico}, url = {/brokenurl#<Go to ISI>://WOS:000418369000027}, doi = {10.1039/c7nj03212a}, issn = {1144-0546}, year = {2018}, date = {2018-01-01}, journal = {New Journal of Chemistry}, volume = {42}, number = {1}, pages = {260-264}, abstract = {The reaction of 2,4-dinitrobenzenesulfonyl chloride toward propylamine was kinetically evaluated in 19 organic solvents and 10 ionic liquids as reaction media. This study was compared with a previous study to experimentally show that solvent effects and the nature of the reacting pair drastically affect the reaction rate and the reaction mechanism. While the reaction of the reference electrophile 2,4-dinitrobenzenesulfonyl chloride with piperidine is favored in polar solvents with the ability to donate or accept hydrogen bonds, the reaction with propylamine is favored in solvents with the ability to accept hydrogen bonds.}, keywords = {amines, aromatic aryl azides, conventional ionic kinetics, liquids, preferential reaction-mechanism, regioselectivity solvation, solvents, substitutions, temperature}, pubstate = {published}, tppubtype = {article} } The reaction of 2,4-dinitrobenzenesulfonyl chloride toward propylamine was kinetically evaluated in 19 organic solvents and 10 ionic liquids as reaction media. This study was compared with a previous study to experimentally show that solvent effects and the nature of the reacting pair drastically affect the reaction rate and the reaction mechanism. While the reaction of the reference electrophile 2,4-dinitrobenzenesulfonyl chloride with piperidine is favored in polar solvents with the ability to donate or accept hydrogen bonds, the reaction with propylamine is favored in solvents with the ability to accept hydrogen bonds. |
2014 |
Cerda-Monje, A; Ormazabal-Toledo, R; Cardenas, C; Fuentealba, P; Contreras, R Regional Electrophilic and Nucleophilic Fukui Functions Efficiently Highlight the Lewis Acidic/Basic Regions in Ionic Liquids Artículo de revista Journal of Physical Chemistry B, 118 (13), pp. 3696-3701, 2014, ISSN: 1520-6106. Resumen | Enlaces | BibTeX | Etiquetas: alkenes, alkynes, aromatic designer diels-alder electrostatic future, knoevenagel, potentials, rationalization reaction, reactivity, solvents, substitutions @article{RN223, title = {Regional Electrophilic and Nucleophilic Fukui Functions Efficiently Highlight the Lewis Acidic/Basic Regions in Ionic Liquids}, author = { A. Cerda-Monje and R. Ormazabal-Toledo and C. Cardenas and P. Fuentealba and R. Contreras}, url = {/brokenurl#<Go to ISI>://WOS:000333948200024}, doi = {10.1021/jp5009994}, issn = {1520-6106}, year = {2014}, date = {2014-01-01}, journal = {Journal of Physical Chemistry B}, volume = {118}, number = {13}, pages = {3696-3701}, abstract = {The origin of catalysis and selectivity induced by room temperature ionic liquids in several organic reactions has putatively been associated with the concept of cation effect (hydrogen bond donor ability of the ionic liquids) or anion effect (hydrogen bond accepting ability of the ionic liquids). We show that there may be cases where this a priori classification may not be correctly assigned. Cations may concentrate both Lewis acidity and basicity functions in one fragment of the ionic liquid: an effect we tentatively call bifunctional distribution of the molecular Lewis acidity/basicity. Bifunctionality on the cation is however anion dependent through electronic polarization effects. The molecular distribution of the Lewis acidity/basicity may simply be assessed by evaluating the regional Fukui function within a reference ion pair structure. The model is tested for a set of nine ionic liquids based on the 1-butyl-3-methylimidazolium cation commonly used as solvent to run organic reactions.}, keywords = {alkenes, alkynes, aromatic designer diels-alder electrostatic future, knoevenagel, potentials, rationalization reaction, reactivity, solvents, substitutions}, pubstate = {published}, tppubtype = {article} } The origin of catalysis and selectivity induced by room temperature ionic liquids in several organic reactions has putatively been associated with the concept of cation effect (hydrogen bond donor ability of the ionic liquids) or anion effect (hydrogen bond accepting ability of the ionic liquids). We show that there may be cases where this a priori classification may not be correctly assigned. Cations may concentrate both Lewis acidity and basicity functions in one fragment of the ionic liquid: an effect we tentatively call bifunctional distribution of the molecular Lewis acidity/basicity. Bifunctionality on the cation is however anion dependent through electronic polarization effects. The molecular distribution of the Lewis acidity/basicity may simply be assessed by evaluating the regional Fukui function within a reference ion pair structure. The model is tested for a set of nine ionic liquids based on the 1-butyl-3-methylimidazolium cation commonly used as solvent to run organic reactions. |
2018 |
Effect of the Nature of the Nucleophile and Solvent on an Snar Reaction Artículo de revista New Journal of Chemistry, 42 (1), pp. 260-264, 2018, ISSN: 1144-0546. |
2014 |
Regional Electrophilic and Nucleophilic Fukui Functions Efficiently Highlight the Lewis Acidic/Basic Regions in Ionic Liquids Artículo de revista Journal of Physical Chemistry B, 118 (13), pp. 3696-3701, 2014, ISSN: 1520-6106. |