Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS−) with piperidine in the presence of cationic micelles

摘要: Pseudo-first-order rate constants (k(obs)) for piperidinolysis of PS- follow the relationship k(obs) - k(0)= k(n)(obs) Pip(T) (Pip(T) = total concentration Pip) at a constant CTABr(T) (total cetyltrimethylammonium bromide), MX (inert salt concentration) and 35 degreesC. The values different CTABrT (ranging from 0.005 to 0.02 M) (k(w)(n) + k(w)(n) Psi KnsM K-N K-S(0)CTABr(T))/( 1 K-S(0) CTABr(T)), where 0, is an empirical parameter CTABr micellar binding in absence MX. magnitude attributed ability X- expel pseudophase aqueous pseudophase. vary order (sodium cinnamate) >Psi 4-methoxybenzoate) 2-chlorobenzoate) (disodium isophthalate) phthalate) sulfate) fumarate). k(M)(ns) (k(M)(ns) k(M)(n)/V-M, k(M)(n) second-order reaction Pip with V-M molar volume M-1 represents are not significantly affected by presence into mixtures.