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| - Control of Substrate Specificity in Polymer-Catalyzed SolvolysisReactions of p-Nitrophenyl Alkanoates by Changing the Buffer System
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| - The substrate specificity in solvolysis reactions of p-nitrophenyl alkanoates 2 (n = 2−18)catalyzed by 4-(dialkylamino)pyridine-functionalized polymer 1 was examined in buffered aqueousmethanol solution at pH 8.0 and 30 °C. The chemical reactivity and substrate specificity in this catalyticsystem were found to be controlled by changing the buffer system. In 1:1 (v/v) methanol−aqueousphosphate buffer solution, macromolecule 1 exhibits substrate specificity for 2 (n = 14) below 1.0 × 10-5unit mol L-1, and the substrate specificity changes from 2 (n = 14) to 2 (n = 12) as the concentration of1 increases to 2.5 × 10-5 unit mol L-1 and changes again from 2 (n = 12) to 2 (n = 10) when theconcentration of 1 increases further to 7.5 × 10-5 unit mol L-1. However, in 1:1 (v/v) methanol−aqueousTris buffer solution, macromolecule 1 was found to demonstrate the same substrate specificity for 2 (n =14) when the concentration of 1 is increased from 5.0 × 10-6 to 1.0 × 10-4 unit mol L-1. The control ofsubstrate specificity by the change of the buffer system is believed to be unprecedented for catalysis ofester solvolysis.
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