Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
The Photochemistry of Tetraalkyl Substituted γ-Keto-olefinesThe photochemistry of 7,8-dihydro-β-ionone (1) in solution is shown to depend on temperature, polarity and viscosity of the solvent. UV. irradiation (λ ≥ 245 nm) in pentane at +25° converts 1 to the isomeric ethers 3 (16%), 5A (48%) and 5B (22%), whereas at -65° 7,8-dihydro-γ-ionone (26) is obtained in 12% yield together with 13% of 3, 12% of 5A and 9% of 5B. The 1n,π*-excitation of 1 in acetonitrile gives similar results. In the more viscous 1,2,3-triacetoxypropane the photoisomerization 1 → 26 takes place even at + 60° (10% yield, cf. 40% at -15°). In alcoholic solvents, however, no formation of 26 is detected, but the hitherto unknown [2+2]-photocycloaddition 1 → 11 can be observed (4% at -7°, 15% at -65S° in 2-propanol). An intermediate e may be involved (Scheme 14). In addition to the photoreactions 1 → 3, 5A, 5B and 11 the isomerization of 1 to the novel spirocyclic ketone 28 takes place in alcoholic solvents only.Photoisomerization 1 → 3 is presumably a photo-ene process involving a stereoselective intramolecular H-transfer. This type of photoisomerization is restricted to cyclic γ-keto-olefines. The tetraalkylated acyclic γ-keto-olefines 14 and 15 photoisomerize exclusively by [2+2]-cycloaddition, independent of the solvent.On 1n,π*-excitation the δ,∊-unsaturated bicyclic ketone 44 undergoes Norrish-Type-II photofragmentation to the diene 45 or isomerizes to the γ, ∊-unsaturated ketone 17. Competition between these two reactions is strongly temperature dependent: photolysis in pentane at -72° yields quantitatively 45, whereas at + 35° only 30% of 45 and 68% of 17 are obtained.UV. irradiation of the novel spirocyclic ketone 28 gives as primary photoproduct the isomeric aldehyde 29, and in a secondary photoreaction the isomeric oxetanes 30A and 30B. Experiments with deuteriated substrates show that the isomerization of type 28 → 29 is stereocontrolled.
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