THE FRIES REARRANGEMENT OF PHENYL ISOBUTYRATE

Phenyl isobutyrate has been found to undergo a normal Fries rearrangement with anhydrous aluminum chloride at 140 °C. to give a mixture of 2-hydroxy-(40%) and 4-hydroxy-isobutyrophenone (11%). When the reaction was carried out in nitrobenzene solution at room temperature the 4-isomer was formed in 86% yield. Methylation of these compounds furnished 2- and 4-methoxy-isobutyrophenone, identical with the compounds obtained by direct acylation of anisole. Reduction of the hydroxy-isobutyrophenones, which were also prepared by direct acylation of phenol, afforded an alternative route to the isobutylphenols. The orientation of each methoxy ketone was verified by oxidation to the corresponding acid.