We studied decarboxylation of 6-nitrobenzisoxazole-3-carboxylate, 1, as a kinetic probe to investigate microinterface properties of aqueous micelles formed by cationic surfactants of increasing head group bulk, i.e., cetyltrialkylammonium bromide, with alkyl = Me (CTABr), Et (CTEABr), n-Pr (CTPABr), n-Bu (CTBABr) and p-octyloxybenzyltrialkylammonium bromide surfactants with alkyl = Me (pOOTABr), n-Pr (pOOTPABr), and n-Bu (pOOTBABr), and the longer p-dodecyloxybenzyltrimethylammonium bromide (pDoTABr) at concentrations higher than 0.05 M. The pseudophase kinetic treatment fails to fit the data that show anomalies with abrupt increases in k(obs) for CTFABr and CTBABr (but not for CTEABr) and with smooth and continuos increase of kob, for all p-alkyloxybenzyltrilakylanifnonium bromides. Abrupt and successive modifications of the micellar interface properties, undergoing only when the polar head or the alkyl chain have some covalent structure, account for the observed kinetic behavior. (C) 2003 Elsevier Science (USA). All rights reserved.