Reactions of aryl acetates with secondary alicyclic amines in ethanol/water mixtures: Effect of the solvent composition on the kinetics and mechanism
Journal
International Journal of Chemical Kinetics
ISSN
0538-8066
1097-4601
Date Issued
2011
Author(s)
Enrique A. Castro
Daniela Millan
Raul Aguayo
José G. Santos
Type
Resource Types::text::journal::journal article
URL Institutional Repository
Abstract
<jats:title>Abstract</jats:title><jats:p>We report a kinetic study on the reactions of secondary alicyclic amines toward 4‐nitrophenyl, 2,4‐dinitrophenyl, and 2,4,6‐trinitrophenyl acetates (<jats:bold>1, 2</jats:bold>, and <jats:bold>3</jats:bold>) in ethanol/water mixtures of different compositions. It is found that (i) the intermediate in the reaction of <jats:bold>1</jats:bold> is stabilized in a mixture of 90 vol% ethanol; (ii) for the reaction of <jats:bold>2</jats:bold>, the mechanism is stepwise in water but concerted in the mixtures; (iii) For the reaction of <jats:bold>3</jats:bold>, the mechanism is concerted along the whole range of composition; (iv) the effect of NO<jats:sub>2</jats:sub> 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</jats:p>
Subjects
structure-reactivity correlations
;
x-substituted benzoates
;
2
;
4
;
6-trinitrophenyl methyl carbonate
;
rate-determining step
;
aqueous-ethanol
;
2
;
4-dinitrophenyl acetate
;
ester aminolysis
;
phenyl carbonate
;
nonleaving group
;
pyridinolysis