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Issue 0, 1967

Liquid-phase photolysis. Part X. Formation of spiro-oxetans by photoaddition of olefins to p-benzoquinone

Abstract

Irradiation of solutions of p-benzoquinone and olefins in benzene gives spiro-oxetans by 1,2-addition of a carbonyl group of the quinone. The following olefins react in this way: cyclohexene, cyclo-octene, cyclo-octa-1,5-diene, cyclo-octatetraene, bicycloheptadiene, oct-1-ene, and oct-2-ene. The adducts readily undergo acid-catalysed rearrangement to hydroxycoumarans, whilst catalytic hydrogenation leads to p-(2-hydroxyalkyl)phenols, and the starting materials are re-formed on pyrolysis, probably through the hydroxycoumarans. They can function as thermal dienophiles, but showed no tendency to undergo photoaddition of a second molecule of olefin.

Quantum yield determinations have shown that the order of photochemical efficiency for formation of the spirooxetan from cyclo-octene through the three relevant electronic transitions in p-benzoquinone is nπ*[gt-or-equal]ππ*[double greater-than, compressed]ππ**. It is concluded that an olefin p-benzoquinone charge-transfer transition is not significantly involved in the photoaddition process, although there is evidence that polarisation complexing between the olefin and p-benzoquinone is important.

Article information


J. Chem. Soc. C, 1967, 383-389
Article type
Paper

Liquid-phase photolysis. Part X. Formation of spiro-oxetans by photoaddition of olefins to p-benzoquinone

D. Bryce-Smith, A. Gilbert and M. G. Johnson, J. Chem. Soc. C, 1967, 383 DOI: 10.1039/J39670000383

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