Kinetics and mechanism of the reactions of S-2,4-dinitrophenyl 4-substituted thiobenzoates with secondary alicyclic amines.
[reaction: see text] The title reactions, in 44 wt % ethanol-water at 25.0 degrees C, exhibit slightly curved Brønsted-type plots (log kN versus pKa of amines) with slopes beta1 = 0.1-0.44 (at high pKa) and beta2 ca. 0.7 (at low pKa). The magnitude of some of these slopes, together with the fact that the curvature center (pKa(0) = 9.5-10.8) does not change with the electronic effects of the benzoyl substituent, suggests that these reactions are not stepwise, but concerted.
Castro
Enrique A
EA
Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago 6094411, Chile. ecastro@puc.cl
Aguayo
Raul
R
Bessolo
Jorge
J
Santos
José G
JG