Photochemical decomposition of phenazone derivatives. Part 7: Mechanism of decomposition in aqueous solutions

Kinetic studies, supplemented by the isolation and identification of the products of decomposition, have proved the process of photochemical decomposition of phenazone derivatives to be a complex reaction, involving several successive parallel reactions, one of which is predominant depending on the concentration of the solution and the atmosphere above it. In an oxygen-free atmosphere and at low concentrations (10(-4) mol/dm3) decomposition is almost wholly the result of second photolysis of zero order to aziridine derivative----aniline----isonitrile. At higher concentrations (10(-3)-10(-2) mol/dm3), the contribution from the reaction of water photoaddition to the double bond C3-C4 increases. Whereas at concentrations of order greater than or equal to 10(-2) mol/dm3, photoisomerization to imidazole derivatives is predominant. In air, one onserves additionally a second reaction of photooxidation to 4-hydroxy-phenazone----1-acetylo-1-methyl-2-phenyl-hydrazine, a reaction of photodemethylation at N2 with simultaneous oxidation to the 4-ketoderivative, and reactions of hydrolysis characteristic for the individual derivatives. The principal primary photolytic reaction for the group of compounds studied consists in cleavage of the N1-N2 bond of the pyrazoline ring.