Counterion‐Induced Cationic Flexible Nanoparticle Catalytic of Piperidinolysis of Phenyl Salicylate

Abstract

AbstractThe removal of PSa− from bulk aqueous phase to the pseudo‐micellar phase by halobenzoate counterion X is responsible for the monotonic increase in kobs (pseudo first‐order rate constants) with the increase in the values of [MX] where MX = sodium salts of 2‐, and 4‐halobenzoic acids. The values of ion exchange constants, or for X = 2‐ and 4‐halobenzoate ions in the presence of tetradecyltrimethylammonium bromide (TTABr) were calculated from the apparent catalytic rate constants, Xkcat which represent the catalytic effect of CFN. Larger values of or were observed for X = 4‐halobenzoate ions than that for X = 2‐halobenzoate ions due to isomeric factors. The values of or determined in the presence of TTABr were compared with previously determined or values in the presence of cetyltrimethylammonium bromide (CTABr). The values of or are nearly 8 ~ 9‐fold larger for 4‐IBz−, 4‐BrBz− and 4‐ClBz− compared to the respective values of X = 2‐IBz−, 2‐BrBz− and 2‐ClBz−. The values of or for X = 4‐FBz− is nearly 3‐fold larger than that for X = 2‐FBz−. The values of or for X = 2‐ and 4‐halobenzoates are significantly smaller in the presence of TTABr than these in the presence of CTABr nanoparticles.