Hydrochloric Acid → 6-Hydroxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one

Participants

Reaction Conditions

Reaction Steps

Dry, pulverulent lithium hydroxide (19.7 mmol, 3 equivalents) is added in one portion to a well-stirred solution of 2′,5′-dihydroxyacetophenone (6.4 mmol) in dry THF (5 ml) at −78° C. under an argon atmosphere. The reaction mixture is stirred at −78° C. for one hour and subsequently at −1° C. for two hours. After re-cooling to −78° C., a solution of 4-methoxybenzoyl chloride (6.5 mmol) in THF (10 ml) is added in one portion. The mixture is stirred at −78° C. for one hour and at room temperature for 4 hours until the starting material has disappeared. The reaction mixture is emptied onto a mixture of ice (150 g) and concentrated HCl (5 ml) and extracted with dichloromethane (3×50 ml). The solvents are removed from the dried extracts, and the residue is dried under reduced pressure for 24 hours. Glacial acetic acid (30 ml) and sulfuric acid (0.2 ml) are added to the residue, and the mixture is heated at 95–100° C. under an argon atmosphere for from 30 minutes to one hour. Approximately one third of the acetic acid is stripped off, and the residue is emptied into water. The precipitated product is filtered, washed and dried and recrystallised from methanol to give 4′-methoxy-6-hydroxyflavone. 1H NMR (500 MHz, d6-DMSO): δ10.08 (br s, OH), 8.02–7.11 (dm, 4H), 7.63 (d, 1H), 7.35 (d, 1H), 7.26 (d, 1H), 6.86 (s, 1H), 3.88 (s, 3H); 13C NMR (62.90 MHz, d6-DMSO): δ176.78 (s), 162.23 (s), 161.93 (s), 154.73(s), 149.24 (s), 127.97 (s), 124.14 (s), 123.44 (s), 122.77 (s), 119.61 (s), 114.46 (s), 107.52 (s), 104.44 (s), 55.43 (s); EI-MS (70 eV) m/e (rel. abund.)=268.0735 (100). The product is colorless and exhibits the UV absorption maximum at λ=322 nm with ε=24790 (in 2-propanol) (cf. FIG. 1).

Provenance & Evidence