INVESTIGATIONS OF REACTIONS OF SELECTED AZAARENES WITH RADICALS IN WATER - 1 - HYDROXYL AND SULFATE RADICALS

The oxidative degradation of binuclear azaarenes is studied in a numbe r of environmentally relevant radical reactions. The comparison betwee n oxidation mechanisms of hydroxyl and sulfate radicals, as well as be tween dark and photoreactions, is done. Most of the products formed ar e identified. With the change from dark to photoreactions of quinoline and isoquinoline, a shift of the oxidation center from the benzene to the pyridine rings is observed. The reaction behavior of the benzodia zines can be derived from the reaction patterns of quinoline and isoqu inoline. The rate constants of second order are determined for the rea ctions of the azaarenes with carbonate radicals. The rate constants an d the differences in the products formed conformably prove the importa nce of the inclusion of excited states in the reaction mechanism. The application of the frontier orbital concept allows an easy interpretat ion. Electron transfer reactions resulting in radical oxygen species a re shown to be product determining in direct photolysis, too.