Reactions of aryl acetates with secondary alicyclic amines in ethanol/water mixtures: Effect of the solvent composition on the kinetics and mechanism |
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| Authors: | Enrique A. Castro Daniela Millan Raul Aguayo Paola R. Campodónico José G. Santos |
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| Affiliation: | 1. Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago 609‐4411, Chile;2. Instituto de Ciencias, Facultad de Medicina, Clínica Alemana Universidad del Desarrollo, Santiago 771‐0162, Chile |
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| Abstract: | We report a kinetic study on the reactions of secondary alicyclic amines toward 4‐nitrophenyl, 2,4‐dinitrophenyl, and 2,4,6‐trinitrophenyl acetates ( 1, 2 , and 3 ) in ethanol/water mixtures of different compositions. It is found that (i) the intermediate in the reaction of 1 is stabilized in a mixture of 90 vol% ethanol; (ii) for the reaction of 2 , the mechanism is stepwise in water but concerted in the mixtures; (iii) For the reaction of 3 , the mechanism is concerted along the whole range of composition; (iv) the effect of ? NO2 outweighs the solvent effect; (v) preferential solvation in the core of reaction can be ruled out. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 687–693, 2011 |
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