| Abstract: | The deacylation of acetylsalicylate and of adipoyldisalicylate in the presence of modified and unmodified poly(ethylenimine)s has been investigated. The kinetics of these reactions have been analyzed in terms of an initial binding step followed by one or two aminolysis steps, and the relevant kinetic parameters have been evaluated. The polymers markedly accelerate the rate of deacylation. Second-order rate constants based on total primary amine concentration for aminolysis by the polymers are 103–105 times larger than those for methylamine. The most striking effect of the polymer has been observed in the two successive aminolysis steps of adipolydisalicylate where the second rate constant is approximately 20-fold greater than the first, presumably because of local proximity factors. |
