MECHANISMS OF EPOXIDATIONS AND CHLORINATIONS OF HYDROCARBONS BY INORGANIC HYPOCHLORITE IN THE PRESENCE OF A PHASE-TRANSFER CATALYST.

Article abstract of DOI:10.1021/ja00364a035

Inorganic hypochlorite in the presence of a quarternary ammonium salt (phase-transfer catalyst) not only epoxidizes several arenes to arene oxides in high yields but also converts toluene to alpha -chlorotoluene, anisole to ring chlorinated anisoles, and alkenes to a complex mixture of chlorinated and oxidized products, including the epoxide. More detailed studies with this system indicate the following: (1) the high-yield conversion of toluenes to benzyl chlorides proceeds with a deuterium isotope effect of 3. 6 and a rho ** plus value of minus 1. 7: (2) p-chloroanisole is the major product from anisole and is formed in a 22-fold greater quantity than o-chloroanisole; (3) the epoxidation of cis- and trans-alkenes is stereoselective but not completely stereospecific; (4) the chlorination of saturated hydrocarbons occurs with a selectivity that is experimentally identical with that of chlorine monoxide.