Kinetics and Mechanism of the Anilinolysis of Aryl 4-Nitrophenyl Carbonates in Aqueous Ethanol

Abstract

[Chemical reaction: See text] The reactions of anilines with 4-nitrophenyl, 4-methylphenyl, and 4-chlorophenyl 4-nitrophenyl carbonates (BNPC, MPNPC and ClPNPC, respectively) are studied kinetically in 44 wt % ethanol-water, at 25.0 degrees C, with an ionic strength of 0.2 M (KCl). Plots of k(obsd) vs [amine] are linear, with the slopes (kN) independent of pH. The Brønsted-type plots (log k(N) vs pKa of conjugate acids of anilines) are linear, with slopes beta = 0.65, 0.85, and 0.78 for the reactions of anilines with BNPC, MPNPC, and ClPNPC, respectively. The values of the slopes for the two latter reactions are in accordance with those obtained in stepwise mechanism where breakdown to product of a zwitterionic tetrahedral intermediate is the rate-determining step. On the other hand, the beta value for the reactions of BNPC is at the upper limit of those found for concerted mechanisms. The kinetic results for the reactions of anilines with BNPC correlates well with those for the concerted reactions of the same amines with 4-methylphenyl and 4-chlorophenyl 2,4-dinitrophenyl carbonates: A plot of the calculated log k(N) values (through a multiple parametric equation) vs the experimental log k(N) values is linear with unity slope and zero intercept, which confirms the concerted mechanism for the latter three reactions.