1,2-Dibromo-4,5-diethoxy-3-fluorobenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 5-bromo-1,2-diethoxy-3-fluorobenzene (40.0 g, 0.15 mol) in acetic acid (200 mL), sodium acetate (16.2 g, 0.20 mol) and bromine (31.6 g, 0.20 mol) were added sequentially at room temperature, and the mixture was stirred at 50° C. for 1.5 hours. The reaction mixture was cooled to room temperature, and a saturated aqueous solution of sodium thiosulfate (400 mL) and water (400 mL) were added sequentially. The mixture was extracted once with heptane (800 mL) and three times with heptane (400 mL). The organic layer was washed sequentially with water (400 mL), once with a 2 N aqueous solution of sodium hydroxide (200 mL), once with a 2 N aqueous solution of sodium hydroxide (100 mL), and water (400 mL), then dried over anhydrous magnesium sulfate. The solvent was distilled off from the organic layer under reduced pressure and the residue was filtered. The filtrate was then purified by silica gel column chromatography (hexane, ethyl acetate) to give 52.0 g of the title compound (yield:quant.). The reaction mixture was cooled to room temperature The mixture was extracted once with heptane (800 mL) and three times with heptane (400 mL) The organic layer was washed sequentially with water (400 mL), once with a 2 N aqueous solution of sodium hydroxide (200 mL), once with a 2 N aqueous solution of sodium hydroxide (100 mL), and water (400 mL) dried over anhydrous magnesium sulfate The solvent was distilled off from the organic layer under reduced pressure the residue was filtered The filtrate was then purified by silica gel column chromatography (hexane, ethyl acetate)

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 5-bromo-1,2-diethoxy-3-fluorobenzene (40.0 g, 0.15 mol) in acetic acid (200 mL), sodium acetate (16.2 g, 0.20 mol) and bromine (31.6 g, 0.20 mol) were added sequentially at room temperature, and the mixture was stirred at 50° C. for 1.5 hours. The reaction mixture was cooled to room temperature, and a saturated aqueous solution of sodium thiosulfate (400 mL) and water (400 mL) were added sequentially. The mixture was extracted once with heptane (800 mL) and three times with heptane (400 mL). The organic layer was washed sequentially with water (400 mL), once with a 2 N aqueous solution of sodium hydroxide (200 mL), once with a 2 N aqueous solution of sodium hydroxide (100 mL), and water (400 mL), then dried over anhydrous magnesium sulfate. The solvent was distilled off from the organic layer under reduced pressure and the residue was filtered. The filtrate was then purified by silica gel column chromatography (hexane, ethyl acetate) to give 52.0 g of the title compound (yield:quant.). The reaction mixture was cooled to room temperature The mixture was extracted once with heptane (800 mL) and three times with heptane (400 mL) The organic layer was washed sequentially with water (400 mL), once with a 2 N aqueous solution of sodium hydroxide (200 mL), once with a 2 N aqueous solution of sodium hydroxide (100 mL), and water (400 mL) dried over anhydrous magnesium sulfate The solvent was distilled off from the organic layer under reduced pressure the residue was filtered The filtrate was then purified by silica gel column chromatography (hexane, ethyl acetate)

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: After dissolving the 1,2-dibromo-4,5-diethoxy-3-fluorobenzene (480 g) in dimethylformamide (1400 ml), copper cyanide (345 g) was added and the mixture was stirred at 150° C. for 3 hours. Saturated aqueous ammonia was added to the reaction mixture, and then the mixture was stirred overnight and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography (solvent: n-hexane-ethyl acetate) to yield the title compound (513 g) as white crystals. was added the mixture was stirred overnight extraction The organic layer was dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure the residue was purified by silica gel column chromatography (solvent: n-hexane-ethyl acetate)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: After dissolving 1,2-dibromo-3-fluoro-4,5-diethoxybenzene (5 g, 14.5 ml) in dichloromethane (70 ml), aluminum chloride (3.9 g, 29.3 mmol) was added while stirring on ice. The mixture was stirred at room temperature for 2 hours 30 minutes, 1 N hydrochloric acid (70 ml) was added and extraction was performed with ethyl acetate (70 ml×2) and then after washing the combined organic layers with brine (50 ml) and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (solvent: n-hexane-ethyl acetate) to obtain the title compound (4.31 g, 94%). was added The mixture was stirred at room temperature for 2 hours 30 minutes extraction after washing the combined organic layers with brine (50 ml) drying over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure The residue was purified by silica gel column chromatography (solvent: n-hexane-ethyl acetate)