5-bromo-2-methylsulfonylaniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 19.5 mmol) in dry tetrahydrofuran (30 mL) at 25° C. was treated with acetyl chloride (6.28 g, 80 mmol). The resulting solution was stirred overnight at 25° C., at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was then diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated, and the aqueous layer was extracted with ethyl acetate (1×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to afford a brown solid. The brown solid was treated with diethyl ether (50 mL) and hexanes (50 mL). The white solid was collected by filtration and washed with hexanes (50 mL) to afford N-(5-bromo-2-methanesulfonyl-phenyl)-acetamide (4.55 g, 80%) as a white solid: mp 157-160° C.; EI-HRMS m/e calcd for C9H10BrNO3S (M+) 290.9565, found 290.9560. The two layers were separated the aqueous layer was extracted with ethyl acetate (1×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo to afford a brown solid The white solid was collected by filtration washed with hexanes (50 mL)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 19.5 mmol) in dry tetrahydrofuran (30 mL) at 25° C. was treated with acetyl chloride (6.28 g, 80 mmol). The resulting solution was stirred overnight at 25° C., at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was then diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated, and the aqueous layer was extracted with ethyl acetate (1×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to afford a brown solid. The brown solid was treated with diethyl ether (50 mL) and hexanes (50 mL). The white solid was collected by filtration and washed with hexanes (50 mL) to afford N-(5-bromo-2-methanesulfonyl-phenyl)-acetamide (4.55 g, 80%) as a white solid: mp 157-160° C.; EI-HRMS m/e calcd for C9H10BrNO3S (M+) 290.9565, found 290.9560. The two layers were separated the aqueous layer was extracted with ethyl acetate (1×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo to afford a brown solid The white solid was collected by filtration washed with hexanes (50 mL)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A light brown suspension of 4-bromo-1-methanesulfonyl-2-nitro-benzene (8.65 g, 30.9 mmol) in methanol (300 mL, not completely dissolved in methanol even at hot condition) was treated sequentially with ammonium chloride (24.8 g, 463.5 mmol), zinc dust (20.2 g, 309 mmol), and water (100 mL). Initially, the reaction was exothermic, and the brown color disappeared. The reaction mixture was stirred for 1 h at 25° C. The reaction mixture was then filtered, and the residue was washed with methanol (50 mL) and ethyl acetate (100 mL). The filtrate was concentrated in vacuo, and the organic compound was extracted into ethyl acetate (3×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. Biotage chromatography (FLASH 40M, Silica, 8/1 to 6/1 to 4/1 hexanes/ethyl acetate) afforded 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 74%) as-a white solid: mp 107-109° C.; EI-HRMS m/e calcd for C7H8BrNO2S (M+) 248.9459, found 248.9451. The reaction mixture was then filtered the residue was washed with methanol (50 mL) and ethyl acetate (100 mL) The filtrate was concentrated in vacuo the organic compound was extracted into ethyl acetate (3×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 19.5 mmol) in dry tetrahydrofuran (30 mL) at 25° C. was treated with acetyl chloride (6.28 g, 80 mmol). The resulting solution was stirred overnight at 25° C., at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was then diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated, and the aqueous layer was extracted with ethyl acetate (1×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to afford a brown solid. The brown solid was treated with diethyl ether (50 mL) and hexanes (50 mL). The white solid was collected by filtration and washed with hexanes (50 mL) to afford N-(5-bromo-2-methanesulfonyl-phenyl)-acetamide (4.55 g, 80%) as a white solid: mp 157-160° C.; EI-HRMS m/e calcd for C9H10BrNO3S (M+) 290.9565, found 290.9560. The two layers were separated the aqueous layer was extracted with ethyl acetate (1×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo to afford a brown solid The white solid was collected by filtration washed with hexanes (50 mL)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 19.5 mmol) in dry tetrahydrofuran (30 mL) at 25° C. was treated with acetyl chloride (6.28 g, 80 mmol). The resulting solution was stirred overnight at 25° C., at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was then diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated, and the aqueous layer was extracted with ethyl acetate (1×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to afford a brown solid. The brown solid was treated with diethyl ether (50 mL) and hexanes (50 mL). The white solid was collected by filtration and washed with hexanes (50 mL) to afford N-(5-bromo-2-methanesulfonyl-phenyl)-acetamide (4.55 g, 80%) as a white solid: mp 157-160° C.; EI-HRMS m/e calcd for C9H10BrNO3S (M+) 290.9565, found 290.9560. The two layers were separated the aqueous layer was extracted with ethyl acetate (1×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo to afford a brown solid The white solid was collected by filtration washed with hexanes (50 mL)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A light brown suspension of 4-bromo-1-methanesulfonyl-2-nitro-benzene (8.65 g, 30.9 mmol) in methanol (300 mL, not completely dissolved in methanol even at hot condition) was treated sequentially with ammonium chloride (24.8 g, 463.5 mmol), zinc dust (20.2 g, 309 mmol), and water (100 mL). Initially, the reaction was exothermic, and the brown color disappeared. The reaction mixture was stirred for 1 h at 25° C. The reaction mixture was then filtered, and the residue was washed with methanol (50 mL) and ethyl acetate (100 mL). The filtrate was concentrated in vacuo, and the organic compound was extracted into ethyl acetate (3×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. Biotage chromatography (FLASH 40M, Silica, 8/1 to 6/1 to 4/1 hexanes/ethyl acetate) afforded 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 74%) as a white solid: mp 107-109° C.; EI-HRMS m/e calcd for C7H8BrNO2S (M+) 248.9459, found 248.9451. The reaction mixture was then filtered the residue was washed with methanol (50 mL) and ethyl acetate (100 mL) The filtrate was concentrated in vacuo the organic compound was extracted into ethyl acetate (3×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 19.5 mmol) in dry tetrahydrofuran (30 mL) at 25° C. was treated with acetyl chloride (6.28 g, 80 mmol). The resulting solution was stirred overnight at 25° C., at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was then diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated, and the aqueous layer was extracted with ethyl acetate (1×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to afford a brown solid. The brown solid was treated with diethyl ether (50 mL) and hexanes (50 mL). The white solid was collected by filtration and washed with hexanes (50 mL) to afford N-(5-bromo-2-methanesulfonyl-phenyl)-acetamide (4.55 g, 80%) as a white solid: mp 157-160° C.; EI-HRMS m/e calcd for C9H10BrNO3S (M+) 290.9565, found 290.9560. The two layers were separated the aqueous layer was extracted with ethyl acetate (1×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo to afford a brown solid The white solid was collected by filtration washed with hexanes (50 mL)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A light brown suspension of 4-bromo-1-methanesulfonyl-2-nitro-benzene (8.65 g, 30.9 mmol) in methanol (300 mL, not completely dissolved in methanol even at hot condition) was treated sequentially with ammonium chloride (24.8 g, 463.5 mmol), zinc dust (20.2 g, 309 mmol), and water (100 mL). Initially, the reaction was exothermic, and the brown color disappeared. The reaction mixture was stirred for 1 h at 25° C. The reaction mixture was then filtered, and the residue was washed with methanol (50 mL) and ethyl acetate (100 mL). The filtrate was concentrated in vacuo, and the organic compound was extracted into ethyl acetate (3×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. Biotage chromatography (FLASH 40M, Silica, 8/1 to 6/1 to 4/1 hexanes/ethyl acetate) afforded 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 74%) as a white solid: mp 107-109° C.; EI-HRMS m/e calcd for C7H8BrNO2S (M+) 248.9459, found 248.9451. The reaction mixture was then filtered the residue was washed with methanol (50 mL) and ethyl acetate (100 mL) The filtrate was concentrated in vacuo the organic compound was extracted into ethyl acetate (3×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 19.5 mmol) in dry tetrahydrofuran (30 mL) at 25° C. was treated with acetyl chloride (6.28 g, 80 mmol). The resulting solution was stirred overnight at 25° C., at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was then diluted with water (100 mL) and ethyl acetate (100 mL). The two layers were separated, and the aqueous layer was extracted with ethyl acetate (1×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to afford a brown solid. The brown solid was treated with diethyl ether (50 mL) and hexanes (50 mL). The white solid was collected by filtration and washed with hexanes (50 mL) to afford N-(5-bromo-2-methanesulfonyl-phenyl)-acetamide (4.55 g, 80%) as a white solid: mp 157-160° C.; EI-HRMS m/e calcd for C9H10BrNO3S (M+) 290.9565, found 290.9560. The two layers were separated the aqueous layer was extracted with ethyl acetate (1×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo to afford a brown solid The white solid was collected by filtration washed with hexanes (50 mL)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A light brown suspension of 4-bromo-1-methanesulfonyl-2-nitro-benzene (8.65 g, 30.9 mmol) in methanol (300 mL, not completely dissolved in methanol even at hot condition) was treated sequentially with ammonium chloride (24.8 g, 463.5 mmol), zinc dust (20.2 g, 309 mmol), and water (100 mL). Initially, the reaction was exothermic, and the brown color disappeared. The reaction mixture was stirred for 1 h at 25° C. The reaction mixture was then filtered, and the residue was washed with methanol (50 mL) and ethyl acetate (100 mL). The filtrate was concentrated in vacuo, and the organic compound was extracted into ethyl acetate (3×100 mL). The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. Biotage chromatography (FLASH 40M, Silica, 8/1 to 6/1 to 4/1 hexanes/ethyl acetate) afforded 5-bromo-2-methanesulfonyl-phenylamine (5.7 g, 74%) as-a white solid: mp 107-109° C.; EI-HRMS m/e calcd for C7H8BrNO2S (M+) 248.9459, found 248.9451. The reaction mixture was then filtered the residue was washed with methanol (50 mL) and ethyl acetate (100 mL) The filtrate was concentrated in vacuo the organic compound was extracted into ethyl acetate (3×100 mL) The combined organic extracts were washed with a saturated aqueous sodium chloride solution (1×200 mL) dried over anhydrous sodium sulfate filtered concentrated in vacuo