Shufletyuk V. The kinetics of tertiary hydroperoxides decomposition in the presence of tetraethylammonium halogenides

It is shown that quaternary onium salts activate the decomposition of hydroperoxides at temperatures below thermolysis one. In the investigated reaction quaternary salts possess of catalytic properties. Results of decomposition of hydroperoxides investigations have showed that the intermediate complex was formed be-tween reactants. For description of catalytic decomposi-tion of hydroperoxides kinetic scheme, including thermal substrate decomposition is proposed. For reaction of hy-droperoxides with quaternary salts values of equilibrium constants of complex formation and constants of its de-composition at different temperatures and activation pa-rameters were obtained. The hydroperoxide catalytic de-composition depend on from a nature both anion and ca-tion salt and structure of hydrocarbon substitute in mole-cule substrate. The investigations of reaction of hydroper-oxide with quaternary salts have shown that the process of decomposition of peroxide bond proceeded with formation of radicals. A main pr oduct of tertiary hydroperoxides and decomposition is ketone. The quantum-chemical analysis of interaction of hydroperoxide with onium salt has con-firmed the formation of the complex between reactants. In the complex the hydroperoxide molecule undergoes a series of essential changes of stereochemical structure and allocation of electron density on atoms. These changes activate hydroperoxide decomposition.