Raksha O. Hydroperoxides decomposition catalyzed by tetraalkylammonium bromides

The present thesis deals with catalytic decomposition of the hydroperoxides in the presence of the tetraalkylammonium bromides. The hydroperoxide and tetraalkylammonium cation structure effect upon the kinetic parameters of the reaction. Activation energies of the hydroperoxides thermolysis and catalytic decomposition have shown to be change simbatically. Chemically activated hydroperoxides decomposition in the presence of Alk4NBr has been shown on the base of kinetic and NMR-spectroscopy data to be proceed through the complexation stage. Decomposition of the complex-bonded hydroperoxides proceeds with lower activation barrier as compared with reaction of their thermal decomposition. 1-hydroxycyclohexyl hydroperoxide in the presence of tetraethylammonium bromide has shown to be the effective low-temperature (308 - 340 K) initiator for the radical chain processes. The structural model has been proposed for the complex of hydroperoxides with Alk4NBr. It includes the hydroperoxide molecule, salt cation and anion, as well as solvent molecule. Structural reorganization of the hydroperoxide fragment is the key factor of the chemical hydroperoxide activation in the presence of Alk4NBr.