Effect of the Migrating Group on the Fries Rearrangement of 4-Biphenylyl 4-Substituted Benzoates〔和文〕

概要

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When a mixture of 4-biphenylyl 4-methylbenzoate(1) and anhydrous aluminum chloride (AlCl3) was boiled in ο-dichlorobenzene, 4-hydroxy-3-biphenylyl 4-methylphenyl ketone(4) was obtained as the main product. The corresponding ο-hydroxyketones, 4-hydroxy-3-biphenylyl 4-chlorophenyl ketone(6) and 4-hydroxy-3-biphenylyl 4-nitrophenyl ketone(8) were also obtained as the main products from 4-biphenylyl 4-chlorobenzoate(2) and 4-biphenylyl 4-nitorobenzoate(3) under the same reaction conditions, in which a small amount of the corresponding 4’-hydroxy-4-biphenylyl ketones(5) were detected. The rate of the Fries rearrangement is as follows; 1>2>3. When the amount of AlCl3 was increased in the Fries rearrangement, the rate formation of 4’-hydroxy-4-biphenylyl phenyl ketones(5, 7, and 9) was accelerated with the decrease in the rate of the ortho-migration. On the other hand, the yield of 8 increased without formation of 9 by increasing of the amount of AlCl3 in the Fries rearrangement of 3. Moreover, 4’-Hydroxy-4-biphenyly ketones(5, 7, and 9) were also obtained in the Fries rearrangement of 1, 2 and 3 using ο-dichlorobenzene at boiling temperature. Ortho-Fries rearrangement of 1, 2 and 3 seems to proceed mainly via an intramolecular pathway slightly accompanied by intermolecular rearrangement.
日本油化学会の論文
2001-08-01