3-fluoro-4-methylsulfonylaniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of 3-fluoro-4-(methylsulfonyl)aniline (8.1 g, 42.9 mmol) in 20% aqueous HCl (27 mL) was added dropwise a solution of sodium nitrite (3 g, 43.5 mmol) in water (20 mL) at 0° C. After stirring for 1 hour, the resulting suspension was added to a solution of sodium sulfite (13.5 g, 110 mmol) in water (60 mL) and 20% aqueous NaOH (3 mL) at 0-5° C. Then the mixture was heated at 60-70° C. for 2 hours, and conc. HCl (3.5 mL) was added. The resulting mixture was heated for further 5 hours at 60° C. After cooling down to room temperature, the mixture was made basic by Na2CO3. The whole was extracted with THF (150 mL×3), the combined organic layer washed with brine (100 mL), dried over MgSO4, and concentarted in vacuo. The resulting solid was recrystallized from EtOH to give 3-fluoro-4-(methylsulfonyl)phenylhydrazine (5 g, 57% yield). The resulting mixture was heated for further 5 hours at 60° C After cooling down to room temperature The whole was extracted with THF (150 mL×3) the combined organic layer washed with brine (100 mL) dried over MgSO4 The resulting solid was recrystallized from EtOH

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3-fluoro-4-(methylsulfonyl)nitrobenzene (8 g, 36.5 mmol), iron powder (22 g, 394 mmol), and acetic acid (0.3 mL) in water (200 mL) was heated at 95° C. for 3 hours. After cooling, insolubles were filtered off by Celite. The filtrate was extracted with ethyl acetate (200 mL×2), the combined organic layer washed with water, brine, dried over MgSO4, and concentrated in vacuo. Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1) provided the subtitle compound (6.2 g, 90% yield). After cooling insolubles were filtered off by Celite The filtrate was extracted with ethyl acetate (200 mL×2) the combined organic layer washed with water, brine dried over MgSO4 concentrated in vacuo Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1)

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of 3-fluoro-4-(methylsulfonyl)aniline (8.1 g, 42.9 mmol) in 20% aqueous HCl (27 mL) was added dropwise a solution of sodium nitrite (3 g, 43.5 mmol) in water (20 mL) at 0° C. After stirring for 1 hour, the resulting suspension was added to a solution of sodium sulfite (13.5 g, 110 mmol) in water (60 mL) and 20% aqueous NaOH (3 mL) at 0-5° C. Then the mixture was heated at 60-70° C. for 2 hours, and conc. HCl (3.5 mL) was added. The resulting mixture was heated for further 5 hours at 60° C. After cooling down to room temperature, the mixture was made basic by Na2CO3. The whole was extracted with THF (150 mL×3), the combined organic layer washed with brine (100 mL), dried over MgSO4, and concentrated in vacuo. The resulting solid was recrystallized from EtOH to give 3-fluoro-4-(methylsulfonyl)phenylhydrazine (5 g, 57% yield). The resulting mixture was heated for further 5 hours at 60° C After cooling down to room temperature The whole was extracted with THF (150 mL×3) the combined organic layer washed with brine (100 mL) dried over MgSO4 concentrated in vacuo The resulting solid was recrystallized from EtOH

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3-fluoro-4-(methylsulfonyl)nitrobenzene (8 g, 36.5 mmol), iron powder (22 g, 394 mmol), and acetic acid (0.3 mL) in water (200 mL) was heated at 95° C. for 3 hours. After cooling, insolubles were filtered off by Celite. The filtrate was extracted with ethyl acetate (200 mL×2), the combined organic layer washed with water, brine, dried over MgSO4, and concentrated in vacuo. Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1) provided the subtitle compound (6.2 g, 90% yield). After cooling insolubles were filtered off by Celite The filtrate was extracted with ethyl acetate (200 mL×2) the combined organic layer washed with water, brine dried over MgSO4 concentrated in vacuo Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1)

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3-fluoro-4-(methylsulfonyl)nitrobenzene (8 g, 36.5 mmol), iron powder (22 g, 394 mmol), and acetic acid (0.3 mL) in water (200 mL) was heated at 95° C. for 3 hours. After cooling, insolubles were filtered off by Celite. The filtrate was extracted with ethyl acetate (200 mL×2), the combined organic layer washed with water, brine, dried over MgSO4, and concentrated in vacuo. Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1) provided the subtitle compound (6.2 g, 90% yield). After cooling insolubles were filtered off by Celite The filtrate was extracted with ethyl acetate (200 mL×2) the combined organic layer washed with water, brine dried over MgSO4 concentrated in vacuo Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1)

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of 3-fluoro-4-(methylsulfonyl)aniline (8.1 g, 42.9 mmol) in 20% aqueous HCl (27 mL) was added dropwise a solution of sodium nitrite (3 g, 43.5 mmol) in water (20 mL) at 0° C. After stirring for 1 hour, the resulting suspension was added to a solution of sodium sulfite (13.5 g, 110 mmol) in water (60 mL) and 20% aqueous NaOH (3 mL) at 0-5° C. Then the mixture was heated at 60-70° C. for 2 hours, and conc. HCl (3.5 mL) was added. The resulting mixture was heated for further 5 hours at 60° C. After cooling down to room temperature, the mixture was made basic by Na2CO3. The whole was extracted with THF (150 mL×3), the combined organic layer washed with brine (100 mL), dried over MgSO4, and concentarted in vacuo. The resulting solid was recrystallized from EtOH to give 3-fluoro-4-(methylsulfonyl)phenylhydrazine (5 g, 57% yield). The resulting mixture was heated for further 5 hours at 60° C After cooling down to room temperature The whole was extracted with THF (150 mL×3) the combined organic layer washed with brine (100 mL) dried over MgSO4 The resulting solid was recrystallized from EtOH

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3-fluoro-4-(methylsulfonyl)nitrobenzene (8 g, 36.5 mmol), iron powder (22 g, 394 mmol), and acetic acid (0.3 mL) in water (200 mL) was heated at 95° C. for 3 hours. After cooling, insolubles were filtered off by Celite. The filtrate was extracted with ethyl acetate (200 mL×2), the combined organic layer washed with water, brine, dried over MgSO4, and concentrated in vacuo. Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1) provided the subtitle compound (6.2 g, 90% yield). After cooling insolubles were filtered off by Celite The filtrate was extracted with ethyl acetate (200 mL×2) the combined organic layer washed with water, brine dried over MgSO4 concentrated in vacuo Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1)

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3-fluoro-4-(methylsulfonyl)nitrobenzene (8 g, 36.5 mmol), iron powder (22 g, 394 mmol), and acetic acid (0.3 mL) in water (200 mL) was heated at 95° C. for 3 hours. After cooling, insolubles were filtered off by Celite. The filtrate was extracted with ethyl acetate (200 mL×2), the combined organic layer washed with water, brine, dried over MgSO4, and concentrated in vacuo. Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1) provided the subtitle compound (6.2 g, 90% yield). After cooling insolubles were filtered off by Celite The filtrate was extracted with ethyl acetate (200 mL×2) the combined organic layer washed with water, brine dried over MgSO4 concentrated in vacuo Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1)

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of 3-fluoro-4-(methylsulfonyl)aniline (8.1 g, 42.9 mmol) in 20% aqueous HCl (27 mL) was added dropwise a solution of sodium nitrite (3 g, 43.5 mmol) in water (20 mL) at 0° C. After stirring for 1 hour, the resulting suspension was added to a solution of sodium sulfite (13.5 g, 110 mmol) in water (60 mL) and 20% aqueous NaOH (3 mL) at 0-5° C. Then the mixture was heated at 60-70° C. for 2 hours, and conc. HCl (3.5 mL) was added. The resulting mixture, was heated for further 5 hours at 60° C. After cooling down to room temperature, the mixture was made basic by Na2CO3. The whole was extracted with THF (150 mL×3), the combined organic layer washed with brine (100 mL), dried over MgSO4, and concentarted in vacuo. The resulting solid was recrystallized from EtOH to give 3-fluoro-4-(methylsulfonyl)phenylhydrazine (5 g, 57% yield). The resulting mixture, was heated for further 5 hours at 60° C After cooling down to room temperature The whole was extracted with THF (150 mL×3) the combined organic layer washed with brine (100 mL) dried over MgSO4 The resulting solid was recrystallized from EtOH

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3-fluoro-4-(methylsulfonyl)nitrobenzene (8 g, 36.5 mmol), iron powder (22 g, 394 mmol), and acetic acid (0.3 mL) in water (200 mL) was heated at 95° C. for 3 hours. After cooling, insolubles were filtered off by Celite. The filtrate was extracted with ethyl acetate (200 mL×2), the combined organic layer washed with water, brine, dried over MgSO4, and concentrated in vacuo. Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1) provided the subtitle compound (6.2 g, 90% yield). After cooling insolubles were filtered off by Celite The filtrate was extracted with ethyl acetate (200 mL×2) the combined organic layer washed with water, brine dried over MgSO4 concentrated in vacuo Chromatographic purification of the residue eluting with ethyl acetate/hexane (1/1)