3-fluoro-4-methylsulfanylaniline

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 10.0 g of 3-fluoro-4-methylsulfanylnitrobenzene prepared in the above example 1, 0.1 eq of Pd/C (5 wt %), 4 eq of amonium formate were dissolved in THF/MeOH (1:1) and refluxed for 3 hours. The solid, which was not dissolved in the solution, was filtered away, and the filtrate was distilled under reduced pressure to obtain oily compound, which was dissolved again in 80 ml of ethyl acetate. Solid amonium formate which was not dissolved in the solution, was filtered away, and the filtrate was distilled under reduced pressure to obtain oily filtrate, which was purified by column chromatography (ethyl acetate:n-Hexane=1:3) to give 6.04 g of the title compound as a yellow solid (yield 88%). refluxed for 3 hours The solid, which was not dissolved in the solution was filtered away the filtrate was distilled under reduced pressure to obtain oily compound, which was filtered away the filtrate was distilled under reduced pressure to obtain oily filtrate, which was purified by column chromatography (ethyl acetate:n-Hexane=1:3)

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 10.0 g of 3-fluoro-4-methylsulfanylnitrobenzene prepared in the above example 1, 0.1 eq of Pd/C (5 wt %), 4 eq of amonium formate were dissolved in THF/MeOH (1:1) and refluxed for 3 hours. The solid, which was not dissolved in the solution, was filtered away, and the filtrate was distilled under reduced pressure to obtain oily compound, which was dissolved again in 80 ml of ethyl acetate. Solid amonium formate which was not dissolved in the solution, was filtered away, and the filtrate was distilled under reduced pressure to obtain oily filtrate, which was purified by column chromatography (ethyl acetate:n-Hexane=1:3) to give 6.04 g of the title compound as a yellow solid (yield 88%). refluxed for 3 hours The solid, which was not dissolved in the solution was filtered away the filtrate was distilled under reduced pressure to obtain oily compound, which was filtered away the filtrate was distilled under reduced pressure to obtain oily filtrate, which was purified by column chromatography (ethyl acetate:n-Hexane=1:3)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Concentrated sulfuric acid (40 mL) was added to a rapidly stirred mixture of 3-fluoro-4-methylsulfanyl-phenylamine (15.5 g, 99 mmol), water (750 mL) and tetrahydrofuran (23 mL). The mixture was cooled to 0° C. and a solution of sodium nitrite (7.5 g, 163 mmol) in water (15 mL) was added. The resulting mixture was stirred for 2 h at 0° C. and it was then added dropwise over 10 min to a stirring solution of copper(II) nitrate (230 g, 1.2 mol) and copper(I) oxide (12.8 g, 89 mmol) in water (1 L). The reaction mixture was stirred for 15 min and then extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried (sodium sulfate), filtered, evaporated, and purified by column chromatography, eluting with 20% ethyl acetate/hexanes to give 3-fluoro-4-methylsulfanyl-phenol (3.73 g, 24%) as a brown oil. The reaction mixture was stirred for 15 min extracted twice with ethyl acetate The combined organic layers were washed with brine dried (sodium sulfate) filtered evaporated purified by column chromatography eluting with 20% ethyl acetate/hexanes

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Iron (33 g, 0.59 mol) was added to 2-fluoro-1-methylsulfanyl-4-nitro-benzene (18.5 g, 99 mmol) in a mixture of acetic acid (350 mL) and water (70 mL). The mixture was stirred for 2 h with periodic swirling, and then the solvents were evaporated. Ethyl acetate and aqueous sodium bicarbonate solution were added and the mixture was filtered through Celite. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried (sodium sulfate), filtered, evaporated, and purified by column chromatography, eluting with 20% ethyl acetate/hexanes to give 3-fluoro-4-methylsulfanyl-phenylamine (15.1 g, 97%). the solvents were evaporated Ethyl acetate and aqueous sodium bicarbonate solution were added the mixture was filtered through Celite The aqueous layer was extracted three times with ethyl acetate The combined organic layers were washed with brine dried (sodium sulfate) filtered evaporated purified by column chromatography eluting with 20% ethyl acetate/hexanes

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 10.0 g of 3-fluoro-4-methylsulfanylnitrobenzene prepared in the above example 1, 0.1 eq of Pd/C (5 wt %), 4 eq of amonium formate were dissolved in THF/MeOH (1:1) and refluxed for 3 hours. The solid, which was not dissolved in the solution, was filtered away, and the filtrate was distilled under reduced pressure to obtain oily compound, which was dissolved again in 80 ml of ethyl acetate. Solid amonium formate which was not dissolved in the solution, was filtered away, and the filtrate was distilled under reduced pressure to obtain oily filtrate, which was purified by column chromatography (ethyl acetate:n-Hexane=1:3) to give 6.04 g of the title compound as a yellow solid (yield 88%). refluxed for 3 hours The solid, which was not dissolved in the solution was filtered away the filtrate was distilled under reduced pressure to obtain oily compound, which was filtered away the filtrate was distilled under reduced pressure to obtain oily filtrate, which was purified by column chromatography (ethyl acetate:n-Hexane=1:3)