CYCLIC ACETALS AS CARBONYL BLOCKING GROUPS IN THE PHOTO-FRIES REARRANGEMENT OF ACYL SUBSTITUTED ARYL ESTERS

Article abstract of DOI:10.1016/S0040-4020(01)96666-9

The ethylene acetals of o and p-acetoxyacetophenone 3a,b, prepared from the corresponding hydroxyacetophenones by treatment with acetic anhydride in pyridine and subsequently with ethylene glycol and p-toluenesulphonic acid, give upon irradiation the expected photo-Fries products 4a,b ( from 3a ) or 6 ( from 3b ). These compounds are converted in part into diacetylphenols 5a,b as a consequence of a deacetalization, occuring to some extent during the irradiation and further in the chromatographic workup. The yields of the photoproducts and the orto/para ratio ( in the case of 3a ) are very similar to those given in the literature forphenyl acetate.By contrast, the acetoxyacetophenones 2a,b do not undergo any appreciable change upon irradiation, showing the deactivating effect of the acetyl side chain.Therefore, it is concluded that cyclic acetals are suitable carbonyl blocking groups in order to circumvent the deactivating effect of acyl substituents on the photo-Fries rearrangement of aryl esters.