Polymer Concentration-Controlled Substrate Specificity in Solvolysis of p-Nitrophenyl Alkanoates Catalyzed by 4-(Dialkylamino)pyridine-Functionalized Polymer in Aqueous Methanol Solution

The substrate specificity in solvolysis reactions of p -nitrophenyl alkanoates 2 ( n = 2−18) catalyzed by 4-(dialkylamino)pyridine-functionalized polymer 1 can be controlled by the concentration of 1 in 50:50 (v/v) methanol−aqueous phosphate buffer solution at pH 8.0 and 30 °C. Below 1.0 × 10 - 5 unit mol L - 1, macromolecule 1 exhibits substrate specificity for 2 ( n =14). As the concentration of 1 increases to 2.5 × 10 - 5 unit mol L - 1, the substrate preference changes from 2 ( n = 14) to 2 ( n = 12). The substrate specificity changes again from 2 ( n = 12) to 2 ( n = 10) when the concentration of 1 increases further to 7.5 × 10 - 5 unit mol L - 1 . The control of substrate specificity by polymer catalyst concentration is believed to be unprecedented for catalysis of ester solvolysis.