Catalyses by polymer complexes, 2. Enhanced esterolytic reactivity of complexes of polymeric soaps and dodecanethiol towards 4‐nitrophenyl acetate

The reaction of dodecanethiol with 4‐nitrophenyl acetate in the presence of dodecyl derivatives of poly(4‐vinylpyridine) and poly(1‐vinyl‐2‐ethylimidazole) was studied at 30°C. It was found that at pH 9,48 the reaction is completed after a few seconds in the presence of polymeric micelles with a content of dodecyl groups > 22 mole‐%, and that the second‐order rate constant amounts to 3,2·103 l mol−1 s−1, which is ca. 150 times higher than that obtained in the absence of the polymer. The reaction rate increases with the content of dodecyl groups in the polymer and the maxima appear at 20 to 30 mole‐%. Polymers substituted with hexyl or ethyl groups instead of dodecyl groups, showed to be virtually ineffective. Obviously, the hydrophobic environment of the polymer activates the bound thiol anion.