Experimental and Theoretical Insights into the Involvement of Radicals in Triclosan Phototransformation

摘要

The phototransformation of triclosan has been a matter of longstanding interest due to both its prevalence in the environment and the discovery of 2,8-dichlorodibenzodiox-in as a photoproduct. In this study, photolysis of triclosan resulted in several primary photoproducts including the following: 2,8-dichlorodibenzodioxin (4%), 4,5'-dichIoro-[1,1'-biphenyl]-2,2'-diol (10%), 5-chloro-2-(4-chlorophenoxy)-phenol (0.5%), and 2,4-dichlorophenol (7%). Trapping studies using d_8-isopropanol showed deuterium incorporation in 5-chloro-2-(4-chlorophenoxy)phenol, providing strong evidence for the involvement of organic radicals in this reaction. Density functional calculations of the excited states of triclosan support the involvement of a radical intermediate in the mechanisms responsible for the dioxin, biphenyl, and phenoxyphenol photoproducts. The pathways for C-CI bond cleavage and cyclization reactions are discussed.