The Fries Rearrangement of 4-Biphenylyl Benzoate and 4-Biphenylyl Acetate

Yoichiro ISOTA*, Nariyuki OHKUBO, Makoto TAKAOKA and Jiro YAMAMOTO

Department of Materials Science, Faculty of Engineering, Tottori University; Koyama-cho, Tottori-shi 680-0945 Japan

When a mixture of 4-biphenylyl benzoate (1) and anhydrous aluminum chloride (AlCl3) was boiled in o-dichlorobenzene, 4-hydroxy-3-biphenylyl phenyl ketone (3) was obtained as a main product together with a small amount of 4'-hydroxy-4-biphenylyl phenyl ketone (4). A rearrangement product 4-hydroxy-3-biphenylyl methyl ketone (5) was given in the reaction of 4-biphenylyl acetate (2) with AlCl3 under the same reaction conditions. Corresponding amounts of 4-biphenylol were obtained as a by-product in the Fries rearrangement of 1 and 2 under the reaction conditions. In these reactions, the reaction of 2 seems to proceed faster than 1. Products distributions (rearrangement products, 3 and 5, and 4-biphenylol) in the Fries rearrangement of 1 and 2 were remarkably different depending upon the reaction temperature. On the other hand, a small amount of 1 and 3 was detected in the reaction of 4 with AlCl3. Fries rearrangement of 1 and 2 may proceed predominantly via an intramolecular pathway.

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