DECOMPOSITION DU PEROXYDE DE BENZOYLE DANS LES MELANGES BENZENE/X-4 PYRIDINES (X=CH3, H, CN). ETUDE CINETIQUE ET INFLUENCE DES SUBSTITUANTS SUR LA REACTIVITE NUCLEOPHILE ET RADICALAIRE DE L'ATOME D'AZOTE

Article abstract of DOI:10.1016/S0040-4020(01)91326-2

Effect of a 4-substituent in the pyridine ring upon the decomposition kinetics of benzoyl peroxide in 4-X pyridine/benzene binary mixtures (X=CH3,H,CN) has been studied.The second-order rate constant for the pyridine-induced decomposition was 2x10^-6 lmol^-1s^-1 and in 4-methylpyridine it was 10^-5 lmol^-1s^-1, a five-fold increase, whereas there was no nucleophilic attack on the peroxide oxygen atoms of benzoyl peroxide by 4-cyanopyridine.The surprisingly high increase of the radical-induced decomposition in 4-cyanopyridine might result from the attack at the nitrogen atom of the pyridine ring by the phenyl radical, the 1-phenylpyridinyl radical being stabilized by the cyano group.