Premium
Correlation analysis of reactivity in the addition of substituted benzylamines to ethyl α‐cyanocinnamate
Author(s) -
Jalani Neeta,
Kothari Seema,
Banerji Kalyan K.
Publication year - 1996
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1996)28:3<165::aid-kin2>3.0.co;2-t
Subject(s) - chemistry , steric effects , reactivity (psychology) , acetonitrile , amine gas treating , medicinal chemistry , kinetics , proton , computational chemistry , stereochemistry , organic chemistry , medicine , physics , alternative medicine , pathology , quantum mechanics
The kinetics of addition of a number of ortho‐, meta‐, and para‐substituted benzylamines to ethyl α‐cyanocinnamate (ECC) in acetonitrile have been studied. The reaction is first‐order with respect to the amine and ECC. The rates of reaction of meta‐ and para‐substituted benzylamines showed excellent correlations with Taft's σ 1 and σ R 0 , and with σ 1 and σ R BA values, respectively. The reaction of the ortho‐compounds showed a very good correlation with Charton's triparametric equation. The reaction is subject to steric hindrance by the ortho‐substituents. A mechanism involving formation of a zwitterionic intermediate in a slow step followed by a fast proton transfer has been proposed. © 1996 John Wiley & Sons, Inc.