4-methylsulfinylaniline

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

Procedure: 2-Iodo-4-fluoronitrobenzene (0.2 mole) and 4-methylsulfinylaniline (0.2 mole) are refluxed in dry dimethylformamide (300 ml.) containing copper powder (5 g) and some powdered potassium carbonate (20 g) under nitrogen for 18 hours. The suspension is filtered, and the organics are washed with water (6 times 100 ml.) in benzene (600 ml.). The benzene layer is extracted with 2.5 N HCl (7×200 ml.), and the acid layer is poured onto powdered sodium bicarbonate. The basic solution is extracted with benzene (6 times 200 ml.), the benzene layer is washed with water (3 times 100 ml.), is separated, dried (MgSO4) and filtered. Evaporation of the solvent followed by chromatography on a 2 in.×24 in. column of silica-gel (Baker), eluted with various proportions of benzene-hexane mixtures, gives pure 5-fluoro-4'-methylsulfinyl-2-nitrobiphenylamine. The suspension is filtered the organics are washed with water (6 times 100 ml.) in benzene (600 ml.) The benzene layer is extracted with 2.5 N HCl (7×200 ml.) the acid layer is poured The basic solution is extracted with benzene (6 times 200 ml.) the benzene layer is washed with water (3 times 100 ml.) is separated dried (MgSO4) filtered Evaporation of the solvent column of silica-gel (Baker), eluted with various proportions of benzene-hexane mixtures

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

Procedure: Following a similar procedure to that described in section a of example 1, but starting from 4-methylsulfinylaniline (obtained in reference example 2) instead of 4-methylsulfonylaniline and from 4-fluoro-3-methoxybenzaldehyde instead of 4-isopropoxybenzaldehyde, the desired compound was obtained, which was directly used in the next step.

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

Procedure: 20 g (143.66 mmol) of 4-methylthioaniline was placed in a flask and dissolved in 660 mL of CH2Cl2. The solution was cooled to 0° C. and 35.42 g (143.66 mmol) of m-chloroperbenzoic acid was added. The mixture was stirred for 3 h at room temperature and poured into CHCl3. It was then washed with saturated NaHCO3 solution, dried over MgSO4 and the solvent was removed, yielding a crude product that was purified by chromatography on silica gel, using MeOH/EtOAc/hexane mixtures of increasing polarity as eluent. The title compound of the example was obtained as a white solid (17.84 g, 80%). It was then washed with saturated NaHCO3 solution dried over MgSO4 the solvent was removed

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

Procedure: 2-Iodo-4-fluoronitrobenzene (0.2 mole) and p-methylsulfinylaniline (0.2 mole) are refluxed in dry dimethylformamide (300 ml.) containing copper powder (5 gm.) and some powdered potassium carbonate (20 gm.) under nitrogen for 18 hours. The solution is filtered and the organics washed with water (6 × 100 ml.) in benzene (600 ml.). The benzene layer is extracted with 2.5 N HCl (7 × 200 ml.) and the acid layer poured onto powdered sodium bicarbonate. The basic solution is extracted with benzene (6 × 200 ml.), the benzene layer washed with water (3 × 100 ml.), separated, dried (MgSO4) and filtered. Evaporation of the solvent followed by chromatography on a 2 in. × 24 in. column of silica-gel (Baker) eluted with various proportions of benzene-hexane mixtures gives pure 5-fluoro-4'-methylsulfinyl-2-nitrobiphenylamine. The solution is filtered the organics washed with water (6 × 100 ml.) in benzene (600 ml.) The benzene layer is extracted with 2.5 N HCl (7 × 200 ml.) the acid layer poured The basic solution is extracted with benzene (6 × 200 ml.) the benzene layer washed with water (3 × 100 ml.) separated dried (MgSO4) filtered Evaporation of the solvent column of silica-gel (Baker) eluted with various proportions of benzene-hexane

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

Procedure: 2-Iodo-4-fluoronitrobenzene (0.2 mole) and p-methylsulfinylaniline (0.2 mole) are refluxed in dry dimethylformamide (300 ml.) containing copper powder (5 gm.) and some powdered potassium carbonate (20 gm.) under nitrogen for 18 hours. The solution is filtered and the organics washed with water (6 × 100 ml.) in benzene (600 ml.). The benzene layer is extracted with 2.5 N HCl (7 × 200 ml.) and the acid layer poured onto powdered sodium bicarbonate. The basic solution is extracted with benzene (6 × 200 ml.), the benzene layer washed with water (3 × 100 ml.), separated, dried (MgSO4) and filtered. Evaporation of the solvent followed by chromatography on a 2 in. × 24 in. column of silica-gel (Baker) eluted with various proportions of benzene-hexane mixtures gives pure 5-fluoro-4'-methylsulfinyl-2-nitrobiphenylamine. The solution is filtered the organics washed with water (6 × 100 ml.) in benzene (600 ml.) The benzene layer is extracted with 2.5 N HCl (7 × 200 ml.) the acid layer poured The basic solution is extracted with benzene (6 × 200 ml.) the benzene layer washed with water (3 × 100 ml.) separated dried (MgSO4) filtered Evaporation of the solvent column of silica-gel (Baker) eluted with various proportions of benzene-hexane

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

Procedure: 2-Iodo-4-fluoronitrobenzene (0.2 mole) and 4-methylsulfinylaniline (0.2 mole) are refluxed in dry dimethylformamide (300 ml.) containing copper powder (5 g) and some powdered potassium carbonate (20 g) under nitrogen for 18 hours. The suspension is filtered, and the organics are washed with water (6 times 100 ml.) in benzene (600 ml.). The benzene layer is extracted with 2.5 N HCl (7×200 ml.), and the acid layer is poured onto powdered sodium bicarbonate. The basic solution is extracted with benzene (6 times 200 ml.), the benzene layer is washed with water (3 times 100 ml.), is separated, dried (MgSO4) and filtered. Evaporation of the solvent followed by chromatography on a 2 in.×24 in. column of silica-gel (Baker), eluted with various proportions of benzene-hexane mixtures, gives pure 5-fluoro-4'-methylsulfinyl-2-nitrobiphenylamine. The suspension is filtered the organics are washed with water (6 times 100 ml.) in benzene (600 ml.) The benzene layer is extracted with 2.5 N HCl (7×200 ml.) the acid layer is poured The basic solution is extracted with benzene (6 times 200 ml.) the benzene layer is washed with water (3 times 100 ml.) is separated dried (MgSO4) filtered Evaporation of the solvent column of silica-gel (Baker), eluted with various proportions of benzene-hexane mixtures

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

Procedure: 2-Iodo-4-fluoronitrobenzene (0.2 mole) and 4-methylsulfinylaniline (0.2 mole) are refluxed in dry dimethylformamide (300 ml.) containing copper powder (5 g) and some powdered potassium carbonate (20 g) under nitrogen for 18 hours. The suspension is filtered, and the organics are washed with water (6 times 100 ml.) in benzene (600 ml.). The benzene layer is extracted with 2.5 N HCl (7×200 ml.), and the acid layer is poured onto powdered sodium bicarbonate. The basic solution is extracted with benzene (6 times 200 ml.), the benzene layer is washed with water (3 times 100 ml.), is separated, dried (MgSO4) and filtered. Evaporation of the solvent followed by chromatography on a 2 in.×24 in. column of silica-gel (Baker), eluted with various proportions of benzene-hexane mixtures, gives pure 5-fluoro-4'-methylsulfinyl-2-nitrobiphenylamine. The suspension is filtered the organics are washed with water (6 times 100 ml.) in benzene (600 ml.) The benzene layer is extracted with 2.5 N HCl (7×200 ml.) the acid layer is poured The basic solution is extracted with benzene (6 times 200 ml.) the benzene layer is washed with water (3 times 100 ml.) is separated dried (MgSO4) filtered Evaporation of the solvent column of silica-gel (Baker), eluted with various proportions of benzene-hexane mixtures

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

Procedure: Following a similar procedure to that described in section a of example 1, but starting from 4-methylsulfinylaniline (obtained in reference example 2) instead of 4-methylsulfonylaniline and from 4-fluoro-3-methoxybenzaldehyde instead of 4-isopropoxybenzaldehyde, the desired compound was obtained, which was directly used in the next step.

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

Procedure: Following a similar procedure to that described in section a of example 1, but starting from 4-methylsulfinylaniline (obtained in reference example 2) instead of 4-methylsulfonylaniline and from 4-fluoro-3-methoxybenzaldehyde instead of 4-isopropoxybenzaldehyde, the desired compound was obtained, which was directly used in the next step.

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

Procedure: 20 g (143.66 mmol) of 4-methylthioaniline was placed in a flask and dissolved in 660 mL of CH2Cl2. The solution was cooled to 0° C. and 35.42 g (143.66 mmol) of m-chloroperbenzoic acid was added. The mixture was stirred for 3 h at room temperature and poured into CHCl3. It was then washed with saturated NaHCO3 solution, dried over MgSO4 and the solvent was removed, yielding a crude product that was purified by chromatography on silica gel, using MeOH/EtOAc/hexane mixtures of increasing polarity as eluent. The title compound of the example was obtained as a white solid (17.84 g, 80%). It was then washed with saturated NaHCO3 solution dried over MgSO4 the solvent was removed

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

Procedure: A mixture of 3.0 g (19 mmol) of 4-methylsulfinylaniline (obtained in reference example 3), 2 mL (19 mmol) of 4-fluorobenzaldehyde and 80 mL of benzene was refluxed in a Dean-Stark for 2 days. The solvent was removed and the crude product obtained was directly used in the next reaction. was refluxed in a Dean-Stark for 2 days The solvent was removed

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

Procedure: Following a similar procedure to that described in reference example 1, but starting from 4-methylthioaniline and using 1 equivalent of m-chloroperbenzoic acid, the title compound of the example was obtained as a white solid (80% yield).