title: Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate in aqueous cationic micelles: kinetic evidence of microinterface property changes.
abstract: 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 CTPABr and CTBABr (but not for CTEABr) and with smooth and continuos increase of k(obs) for all p-alkyloxybenzyltrilakylammonium 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.
authors.affiliation: Dipartimento di Chimica, Università di Perugia, Via Elce di Sotto, 8, 06123 Perugia, Italy.
authors.forename: Lucia
authors.initials: L
authors.lastname: Brinchi
authors.forename: Raimondo
authors.initials: R
authors.lastname: Germani
authors.forename: Gianfranco
authors.initials: G
authors.lastname: Savelli
authors.forename: Luisa
authors.initials: L
authors.lastname: Marte