Photochemistry of dibenzo-1,4-dioxins: intramolecular rearrangement-reduction through observable 2,2′-biphenylquinones

The photochemistry of dibenzo-1,4-dioxin (7) and 2,3,7,8-tetramethyldibenzo-1,4-dioxin (15) — both of which have the parent ring system of the well-known enrimental contaminant dioxin— has been studied in aqueous solution and in selected organic solvents. It is shown that a novel intramolecular photorearrangement is the major mode of reaction for 7 and the exclusive reaction for 15, giving rise to observable (by UV—Vis spectrophotometry) intermediate 2,2′-biphenylquinones. Subsequent reduction by the organic co-solvent gives rise to 2,2′-biphenols as major or exclusive product. Thus, photolysis of these compounds generates oxidizing agents in the biphenylquinones. Photolysis in the presence of added N_aBH₄ resulted is greatly enhanced yields of biphenols along with more than 90% material balance. These findings have relevance to dioxin photodecomposition, which can be used as a method for its destruction.