Fluorinated Fries rearrangement

The Fries rearrangement of fluorophenyl acetates T4to fluorine-containing o- or/t-acetylphenols 15 or 16, respectively, has been carried out with aluminum trichloride13 lh and more recently with alumina and mcthanesulfonic acid.17... 

In this contribution we have presented the synthesis of the new photoreactive thiol MUAP bearing a photoreactive phenyl ester. This molecule is well suited for the preparation of SAMs on gold substrates and can be photochemically modified by UV-illumination due to the photo-Fries rearrangement leading to the formation of hydroxyketones. By a subsequent post-modification reaction with a fluorinated compound low-energy surfaces are attainable. 

The Fries rearrangement of phenyl acetate (PA) over solid-acid catalysts was first studied in a fixed bed reactor at 400 °C by Pouilloux et al. [9,10]. o- and p-Hydro-xyacetophenone (o- and p-HAP), p-acetoxyacetophenone (p-AXAP), and phenol (P) were the main reaction products. Fluorinated alumina and H-FAU zeolites afforded approximately the same product distribution, o-HAP being highly favored over the para isomer. The reaction scheme proposed was that PA dissociates into phenol (P) and ketene and that o-HAP results partly from an intramolecular rearrangement of PA and partly from transacylation (Eq. 2) whereas p-HAP results from the latter reaction only [10]. 

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