Issue 11, 2005

Photochemical rearrangement of dibenzo[1,4]dioxins proceeds through reactive spirocyclohexadienone and biphenylquinone intermediates

Abstract

Photochemical studies on a range of model dibenzo[1,4]dioxins were performed in aqueous and organic solutions. The compounds were found to undergo a photochemically initiated aryl–ether bond homolysis that yields reactive 2-spiro-6′-cyclohexa-2′,4′-dien-1′-one and subsequent 2,2′-biphenylquinone intermediates. Under steady-state irradiation, the 2,2′-biphenylquinones were observed to participate in excited state hydrogen abstraction from the organic solvent to give the corresponding 2,2′-dihydroxybiphenyls. In the absence of continued irradiation, 2,2′-biphenylquinones with electron donating substituents thermally rearrange to the corresponding oxepino[2,3-b]benzofurans, whereas the unsubstituted 2,2′-biphenylquinone and its derivatives with electron withdrawing groups thermally rearrange to the corresponding 1-hydroxydibenzofurans.

Graphical abstract: Photochemical rearrangement of dibenzo[1,4]dioxins proceeds through reactive spirocyclohexadienone and biphenylquinone intermediates

Supplementary files

Article information

Article type
Paper
Submitted
14 Apr 2005
Accepted
11 Aug 2005
First published
09 Sep 2005

Photochem. Photobiol. Sci., 2005,4, 876-886

Photochemical rearrangement of dibenzo[1,4]dioxins proceeds through reactive spirocyclohexadienone and biphenylquinone intermediates

S. Rayne, R. Sasaki and P. Wan, Photochem. Photobiol. Sci., 2005, 4, 876 DOI: 10.1039/B505244K

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