title: Rate constants for the beta-elimination of tosyl radical from a variety of substituted carbon-centered radicals.
abstract: The rate constants for the beta-elimination of tosyl radical (Ts*) from a series of carbon-centered radicals have been determined by using the radical clock methodology. Depending on the substituents R in Ts-CH(2)-CH*R radicals, the rate constants at 293 K vary by more than 2 orders of magnitude in the range of 10(3)-10(6) s(-1). The lowest values were found for the 2-naphthyl and carbamoyl substituents, whereas the benzyl substituent is located at the other extremity. The effect of the substituent upon the stabilization of the starting radical exerts a predominant influence in this reaction in decreasing the rate of fragmentation.
authors.affiliation: Laboratoire de Chimie Moléculaire Organique, UMR 6517, Boite 562, Faculté des Sciences St Jérôme, Université d'Aix-Marseille III, Av. Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France.
authors.forename: Vitaliy I
authors.initials: VI
authors.lastname: Timokhin
authors.forename: Stéphane
authors.initials: S
authors.lastname: Gastaldi
authors.forename: Michèle P
authors.initials: MP
authors.lastname: Bertrand
authors.forename: Chryssostomos
authors.initials: C
authors.lastname: Chatgilialoglu