| Abstract: | The major photoproducts observed in the photolysis of diuron 3-(3,4-dichlorophenyl)-1,1-dimethylurea] ( 2 ) in aqueous solution resulted from a heterolytic substitution of chlorine by OH (photohydrolysis). A wavelength effect was observed: at 254 nm the formation of 3-(4-chloro-3-hydroxyphenyl)-1,1-dimethylurea ( 3 ) accounted for more than 90% of the conversion, whereas when the solution was irradiated in ‘black light’ (85% of photons emitted at 365 nm, about 7% at 334 nm), the major photoproduct was 3-(3-chloro-4-hydroxyphenyl)-1,1-dimethylurea ( 4 ). The presence of methanol favoured the photoreduction into 3-(3-chlorophenyl)-1,1-dimethylurea ( 5 ). Completely different reactions were observed when 2 was irradiated in dry aerobic conditions on silica. They resulted from elimination or oxidation of methyl groups. The main photoproducts initially formed were 3-(3,4-dichlorophenyl)-1-methyl urea ( 6 ) and 3-(3,4-dichlorophenyl)-1-formyl-1-methylurea ( 7 ). In the second stage ( 6 ) was transformed into (3,4-dichlorophenyl)-urea ( 8 ) and 3-(3,4-dichlorophenyl)-1-formylurea ( 9 ); some other minor products such as monuron ( 1 ) were also identified. The formation rate of 6 and 7 was much slower on clay (montmorillonite or kaolin) than on silica. In contrast with products 6 and 8 , the formation of 7 and 9 needed the presence of oxygen: they did not appear when diuron was irradiated in deoxygenated C2Cl3F3. It can be concluded that the photolysis of diuron is highly dependent on the conditions of irradiation. © 1997 SCI. |
