4-fluoro-2-phenylmethoxyaniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:76.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of iron powder (90.36 g, 1.62 mol) and acetic acid (10%, 400 mL) at 80° C. was added a solution of the title compound of Step A (40 g, 0.162 mol) in ethyl acetate (200 mL) dropwise with vigorous stirring. The reaction mixture was stirred further at 76° C. for 1 h. After the reaction was complete, the hot reaction mixture was filtered through Celite® (200 g) and the filter cake was washed with ethyl acetate (1000 mL). The filtrate was washed with water (3×200 mL), sodium bicarbonate solution (5%, 3×200 mL), dried (MgSO4) and concentrated to give the crude product. The product was purified by flash chromatography to give 24.76 g of the title compound of Step B. 1H NMR (CDCl3, 400 MHz): δ 7.41 (m,5H), 6.60 (m,3H), 5.04 (s,2H). the hot reaction mixture was filtered through Celite® (200 g) the filter cake was washed with ethyl acetate (1000 mL) The filtrate was washed with water (3×200 mL), sodium bicarbonate solution (5%, 3×200 mL) dried (MgSO4) concentrated to give the crude product The product was purified by flash chromatography

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

実験手順: To a stirred solution of 2-benzyloxy-4-fluoro-1-nitrobenzene (2.4 g, 10 mmol) in EtOH (20 mL) is added SnCl2 (9.45 g, 50 mmol) and the suspension is stirred at RT overnight. The solvent is removed under reduced pressure and the residue is adjusted to pH >8. The aqueous layer is extracted with EtOAc and the combined organic layers are washed with water and brine, then dried over MgSO4 and filtered. The solvent is removed under reduced pressure to give the product as a red oil. The solvent is removed under reduced pressure The aqueous layer is extracted with EtOAc the combined organic layers are washed with water and brine dried over MgSO4 filtered The solvent is removed under reduced pressure

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To an ethanol (25 mL)-water (25 mL) mixture containing 2-(benzyloxy)-4-fluoro-1-nitrobenzene obtained were added iron (2.79 g, 50.0 mmol) and ammonium chloride (535 mg, 10.0 mmol) at room temperature, and the mixture was stirred at 100° C. for 1 hr. After cooling to room temperature, the reaction mixture was filtered through Celite (registered trademark) and the filtrate was concentrated under reduced pressure. Saturated aqueous sodium hydrogen carbonate solution was added to the resulting residue, and the mixture was extracted three times with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate and then the desiccant was filtered off, followed by concentration under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1) to afford the title compound as a brownish red oil (1.26 g). obtained After cooling to room temperature the reaction mixture was filtered through Celite (registered trademark) the filtrate was concentrated under reduced pressure Saturated aqueous sodium hydrogen carbonate solution was added to the resulting residue the mixture was extracted three times with ethyl acetate The organic layer was washed with brine dried over anhydrous magnesium sulfate the desiccant was filtered off followed by concentration under reduced pressure The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1)

反応条件: temp:76.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of iron powder (90.36 g, 1.62 mol) and acetic acid (10%, 400 mL) at 80° C. was added a solution of the title compound of Step A (40 g, 0.162 mol) in ethyl acetate (200 mL) dropwise with vigorous stirring. The reaction mixture was stirred further at 76° C. for 1 h. After the reaction was complete, the hot reaction mixture was filtered through Celite® (200 g) and the filter cake was washed with ethyl acetate (1000 mL). The filtrate was washed with water (3×200 mL), sodium bicarbonate solution (5%, 3×200 mL), dried (MgSO4) and concentrated to give the crude product. The product was purified by flash chromatography to give 24.76 g of the title compound of Step B. 1H NMR (CDCl3, 400 MHz): δ 7.41 (m,5H), 6.60 (m,3H), 5.04 (s,2H). the hot reaction mixture was filtered through Celite® (200 g) the filter cake was washed with ethyl acetate (1000 mL) The filtrate was washed with water (3×200 mL), sodium bicarbonate solution (5%, 3×200 mL) dried (MgSO4) concentrated to give the crude product The product was purified by flash chromatography

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:76.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of iron powder (90.36 g, 1.62 mol) and acetic acid (10%, 400 mL) at 80° C. was added a solution of the title compound of Step A (40 g, 0.162 mol) in ethyl acetate (200 mL) dropwise with vigorous stirring. The reaction mixture was stirred further at 76° C. for 1 h. After the reaction was complete, the hot reaction mixture was filtered through Celite® (200 g) and the filter cake was washed with ethyl acetate (1000 mL). The filtrate was washed with water (3×200 mL), sodium bicarbonate solution (5%, 3×200 mL), dried (MgSO4) and concentrated to give the crude product. The product was purified by flash chromatography to give 24.76 g of the title compound of Step B. 1H NMR (CDCl3, 400 MHz): δ7.41 (m,5H), 6.60 (m,3H), 5.04 (s,2H). the hot reaction mixture was filtered through Celite® (200 g) the filter cake was washed with ethyl acetate (1000 mL) The filtrate was washed with water (3×200 mL), sodium bicarbonate solution (5%, 3×200 mL) dried (MgSO4) concentrated to give the crude product The product was purified by flash chromatography

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

実験手順: To a stirred solution of 2-benzyloxy-4-fluoro-1-nitrobenzene (2.4 g, 10 mmol) in EtOH (20 mL) is added SnCl2 (9.45 g, 50 mmol) and the suspension is stirred at RT overnight. The solvent is removed under reduced pressure and the residue is adjusted to pH >8. The aqueous layer is extracted with EtOAc and the combined organic layers are washed with water and brine, then dried over MgSO4 and filtered. The solvent is removed under reduced pressure to give the product as a red oil. The solvent is removed under reduced pressure The aqueous layer is extracted with EtOAc the combined organic layers are washed with water and brine dried over MgSO4 filtered The solvent is removed under reduced pressure

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To an ethanol (25 mL)-water (25 mL) mixture containing 2-(benzyloxy)-4-fluoro-1-nitrobenzene obtained were added iron (2.79 g, 50.0 mmol) and ammonium chloride (535 mg, 10.0 mmol) at room temperature, and the mixture was stirred at 100° C. for 1 hr. After cooling to room temperature, the reaction mixture was filtered through Celite (registered trademark) and the filtrate was concentrated under reduced pressure. Saturated aqueous sodium hydrogen carbonate solution was added to the resulting residue, and the mixture was extracted three times with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate and then the desiccant was filtered off, followed by concentration under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1) to afford the title compound as a brownish red oil (1.26 g). obtained After cooling to room temperature the reaction mixture was filtered through Celite (registered trademark) the filtrate was concentrated under reduced pressure Saturated aqueous sodium hydrogen carbonate solution was added to the resulting residue the mixture was extracted three times with ethyl acetate The organic layer was washed with brine dried over anhydrous magnesium sulfate the desiccant was filtered off followed by concentration under reduced pressure The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=9:1)

反応条件: temp:76.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of iron powder (90.36 g, 1.62 mol) and acetic acid (10%, 400 mL) at 80° C. was added a solution of the title compound of Step A (40 g, 0.162 mol) in ethyl acetate (200 mL) dropwise with vigorous stirring. The reaction mixture was stirred further at 76° C. for 1 h. After the reaction was complete, the hot reaction mixture was filtered through Celite® (200 g) and the filter cake was washed with ethyl acetate (1000 mL). The filtrate was washed with water (3×200 mL), sodium bicarbonate solution (5%, 3×200 mL), dried (MgSO4) and concentrated to give the crude product. The product was purified by flash chromatography to give 24.76 g of the title compound of Step B. 1H NMR (CDCl3, 400 MHz): δ 7.41 (m,5H), 6.60 (m,3H), 5.04 (s,2H). the hot reaction mixture was filtered through Celite® (200 g) the filter cake was washed with ethyl acetate (1000 mL) The filtrate was washed with water (3×200 mL), sodium bicarbonate solution (5%, 3×200 mL) dried (MgSO4) concentrated to give the crude product The product was purified by flash chromatography