Pyrogallol → 3,4-Dihydroxy-xanthone

Participants

Reaction Steps

To a stirring solution of 2-fluorobenzoic acid (5.09 g, 36.3 mmol) and dichloromethane (110 mL) in an ice bath under argon was added dropwise a solution of oxalyl chloride (2.0 M in dichloromethane, 21 mL, 42 mmol), followed by dimethylformamide (6 drops). The ice bath was removed and the solution was stirred at room temperature for 1.5 h. The solution was then concentrated by rotary evaporation. The product was dissolved in hexane (3×50 mL) and the mixture was filtered. The filtrate was rotary evaporated to yield 5.42 g of colorless oil. The oil was added dropwise to a mixture of pyrogallol (6.48 g, 51.3 mmol), aluminum chloride (14.6 g, 110 mmol), chloroform (250 mL) and dichloromethane (700 mL), and the solution was stirred for 17 h at room temperature. The solution was then refluxed for 3 h and cooled to room temperature. The solution was washed with 1 N HCl (3×500 mL). The organic layer was filtered, dried over sodium sulfate, and evaporated to yield an oil. The oil was added to dimethylformamide (120 mL) with sodium carbonate (8.11 g, 76.5 mmol) and it was refluxed for 3.5 h. The solution was concentrated by rotary evaporation with heating, and the residue was purified by column chromatography (95:5 chloroform/methanol) to give a solid. The solid was washed with hexane (2×35 mL), filtered and dried to yield 2.10 g (25 %) of the title compound as an off-white solid. 1H NMR (DMSO-d6, 300 MHz): δ 8.16 (d, J=7.42 Hz, 1H), 7.84 (t, J=7.69 Hz, 1H), 7.64 (d, J=8.52 Hz, 1H), 7.57 (d, J=8.79 Hz, 1H), 7.44 (t, J=7.41 Hz, 1H), 6.94 (d, J=8.52 Hz, 1H).

Provenance & Evidence