Kinetics and Mechanism of Alkaline Hydrolysis of Y-Substituted Phenyl Phenyl Carbonates

Second-order rate constants (k(OH-)) have been measured spectrophotometrically for alkaline hydrolysis of Y-substituted phenyl phenyl carbonates (2a-j) and compared with the k(OH-) values reported previously for the corresponding reactions of Y-substituted phenyl benzoates (1a-j). Carbonates 2a-j are 8 similar to 16 times more reactive than benzoates 1a-j. The Hammett plots correlated with sigma(-) and sigma degrees constants exhibit many scattered points, while the Yukawa-Tsuno plot results in excellent linear correlation with rho = 1.21 and r = 0.33. Thus, the reaction has been concluded to proceed through a concerted mechanism in which expulsion of the leaving group is advanced only a little. However, one cannot exclude a possibility that the current reaction proceeds through a forced concerted mechanism with a highly unstable intermediate.