Surfactant-assisted UV-photolysis of nitroarenes

Photochemical transformations (lambda-254 nm) of 2,4-dinitrotoluene (2,4-DNT) in aqueous solutions containing the cationic surfactant cetyltrimethylammonium (CTA) and the anionic nucleophile borohydride (BH4-) were investigated. The overall decay rate was enhanced at CTA concentrations above the critical micelle concentration (cmc) when stoichiometric excess BH4- was present in solution. A kinetic model that separates the overall reaction rate into micellar and aqueous pseudo-phase components indicates transformation in micelles is 17 times faster that in the homogeneous water phase under those conditions investigated. Intermediate products were identified by comparing the HPLC retention times and ultraviolet-visible absorption spectra of product peaks to those of analytical standards. 2-Methyl-5-nitroaniline, 4-nitrotoluene, 2-nitrotoluene, 4-methyl-3-nitroaniline, 2,4-diaminotoluene, o-toluidine, 1,3-dinitrobenzene, 3-nitroaniline, p-cresol, and 2,4-diaminophenol were identified as photo-transformation intermediates or products.