Kinetics of aminolysis of 2,4-dinitrophenyl acetate

Abstract

The second order rate constants for the reaction of 2,4-dinitrophenyl acetate with aniline and <em>p</em>- and <em>o</em>-substituted anilines have been reported in 10% acetonitrile-90% water (v/v) mixture at 25°, 30°, 35° and 40°C. In the reaction of <em>p</em>-substituted anilines, electron-releasing groups facilitate the reaction while electron-withdrawing groups retard it. The <em>ρ</em>-value is evaluated to be - 2.33 ± 0.16. The Bronsted plot is also linear with β_N = 0.792 ± 0.027 at 30°C. The <img src='http://www.niscair.res.in/jinfo/delta.gif' border=0><em>S^≠ </em>values are all negative as expected for bimolecular nucleophilic substitution reactions. In the case of <em>o</em>-substituted anilines, the rate data have been analysed in terms of electronic and steric effects.