title: Promoting mechanistic changes: solvolysis of benzoyl halides in nonionic microemulsions.
abstract: Solvolysis of benzoyl halides has been studied in nonionic isooctane/Brij30/water microemulsions. The reaction takes place only at the microemulsion interface due to the low solubility of benzoyl halides. The variation of the properties (water content and hydration water nucleophilic character) of the microemulsion interface as the amount of water in the system decreases favors mechanistic changes in the solvolytic reaction. The true rate and equilibrium constants at the interface were obtained by means of the formalism of the pseudophase. Rate constant values at the interface change as the water content of the microemulsion is modified. The changes are consistent with a shift of mechanism from dissociative toward associative. The predominance of either dissociative or associative mechanism is dependent on the characteristics of the leaving group. The associative character decreases as the salient group of the benzoyl halides improves. Moreover, the associative pathway is strongly favored in the microemulsion system studied.
authors: Department of Physical Chemistry, Faculty of Chemistry, University of Vigo, 36200 Vigo, Spain.
authors: P
authors: P
authors: Campos-Rey
authors: C
authors: C
authors: Cabaleiro-Lago
authors: P
authors: P
authors: Hervés