RADIOLYSIS OF 2-CHLOROBENZONITRILE, 3-CHLOROBENZONITRILE AND 4-CHLOROBENZONITRILE IN AQUEOUS-SOLUTION AND PRODUCT ANALYSIS

Steady-state radiolysis of 2-, 3-, and 4-chlorobenzonitriles under var ious experimental conditions and HPLC-analysis of the resulting major products were performed. The initial G-values(Gi) of the products have been determined. Hydrated electrons (e(aq)(-)) react with the substra tes forming the corresponding radical anions which decay by dehalogena tion, yielding cyanophenyl radicals, in the presence of a H-donor (e.g . t-butanol) they form benzonitrile, the only product identified. At h igher concentrations the cyanophenyl radicals may also undergo oligome rization.-H-atoms are also found to react with the three chlorobenzoni triles, but no product could be identified. Attack of OK-radicals was found to occur preferably on the position with the highest electron de nsity. Several final products are identified in this case. Also the re actions with the primary products of the water radiolysis in the prese nce of air have been studied. Based on the experimental data some prob able reaction mechanisms were postulated. (C) 1998 Elsevier Science Lt d. All rights reserved.