Catalysis by Hydrophobically Modified Poly(propylenimine) Dendrimers Having Quaternary Ammonium and Tertiary Amine Functionality

Four different quaternary ammonium chloride-modified poly(propylenimine) (PPI) dendrimers were synthesized by alkylation of a PPI dendrimer having eight dimethylamino end groups with 1-bromooctane or 1-bromododecane. By varying the mole ratio ofalkyl bromide to dendrimer, averages of 4-10 quaternary ammonium groups were formed. The new amphiphilic dendrimers are surface active and are micellar catalysts in water. The dendrimers have critical aggregation concentrations between 8.5 x 10 - 4 and 9.0 × 10 - 5 M. Decarboxylation of6-nitrobenzisoxazole-3-carboxylate at 25 °C was 650 times faster than in water alone in the presence of a dendrimer quaternized with eight dodecyl chains at a concentration of 2.45 mM in quaternary ammonium groups. The order of the catalytic efficiency of the new dendrimers decreased with the length and number of hydrophobic alkyl groups in the order (C 1 2 ) 8 > (C 1 2 ) 4 > (C 8 ) 1 0 > (C 8 ) 5 . The pseudo-first-order rate constants for basic hydrolysis of p-nitrophenyl hexanoate in pH 9.4 buffer at 30 °C using the (C 1 2 ) 8 and (C 1 2 ) 4 dendrimers were 26 and 13 times higher than those for hydrolysis with no dendrimer. The kinetic data were fit to a single-site binding model to evaluate the contributions of binding constants of reactants to the dendrimers and catalytic rate constants of the bound species to the overall catalytic activity.