Synthesis and some reactions of organoantimony peroxides of the type (C6H5)4SbOOR?

Abstract

1. By the reactions of anhydrous salts of hydroperoxides with tetraphenylstibonium bromide we obtained and characterized organoantimony peroxides of structure (C6H5)4SbOOR', in which R'=(CH3)3C, (CH3)2 ·C6H5C, CH3(C6H5)2C, and (C6H5)3C. 2. A study was made of the thermal decomposition of the peroxides in which R'=(CH3)3C and (CH3)2 · C6H5C. This goes by an intramolecular rearrangement mechanism with migration of a phenyl group from antimony to oxygen. The solvent does not take part in the reaction, but it affects the reaction rate. 3. Under UV irradiation the reaction of (C6H5)4SbOOC(CH3)3 goes by a free-radical mechanism. The solvent participates in the reaction. The photoreaction of the peroxide in toluene goes with the cleavage of the O-O bond. The reaction products are (C6H5)3SbO, benzene, t-butyl alcohol, and a mixture of isomeric methylbiphenyls. For the photochemical reaction of the peroxide in CC14 and CHCl3 it is suggested that the breakdown of the peroxide is initiated by radicals from the solvent. Reaction in CC14 leads mainly to the formation of tetraphenylstibonium chloride. In CHC13 initiated breakdown of the peroxide and reaction with cleavage of the O-O bond go simultaneously.