Studies of the Selective O-Alkylation and Dealkylation of Flavonoids. VI. Demethylation of 8-Hydroxy-5,7-dimethoxyflavones with Anhydrous Aluminum Chloride or Bromide in Acetonitrile

Article abstract of DOI:10.1246/bcsj.56.3773

The demethylation of seven 8-hydroxy-5,7-dimethoxyflavones with anhydrous aluminum chloride or bromide in acetonitrile was studied and the following results were obtained. (1) Anhydrous aluminum chloride in acetonitrile selectively split the 5-methoxyl group without cleavage of the 7-methoxyl group, and seven 5,8-dihydroxy-7-methoxy-flavones were quantitatively synthesized by the demethylation. (2) In the demethylation with anhydrous aluminum bromide, the 5- and 7-methoxyl groups on 4',5,7-trimethoxy- and 3',4',5,7-tetramethoxy-8-hydroxyflavone were selectively split to give the corresponding 5,7,8-trihydroxyflavones in good yield.However, the demethylation was not accessible to the synthesis of 5,7,8-trihydroxy-3',4',5'-trimethoxyflavone, 4',5,7,8-tetrahydroxy-3'-methoxy-, and 3',5,7,8-tetrahydroxy-4'-methoxyflavone, because of the cleavage of the methoxyl groups on the B ring.The synthesized flavones were employed for the identification of the two natural flavones, which were proposed to be 4',5,8-trihydroxy-7-methoxyflavone and 4',5,8-trihydroxy-3',7-dimethoxyflavone.The former, salvitin, was revised to 4',5,7-trihydroxy-6-methoxyflavone and the latter seemed to be 4',5,7-trihydroxy-3',8-dimethoxyflavone.