4-methylsulfinylphenol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 4-methanesulfinyl-phenol (1.52 g, 9.7 mmol) in DMF (30 ml) cesium carbonate (4.2 g, 12.9 mmol) was added, followed by addition of 5-bromo-2-nitro pyridine (1.75 g, 8.6 mmol) and the mixture was stirred at 50° C. over night. The suspension was filtered and evaporated+co-evaporated with toluene. The compound was purified by chromatography (0→10% EtOH in Methylene chloride) to give 1.5 g (56%) of 5-(4-Methanesulfinyl-phenoxy)-2-nitro-pyridine. The suspension was filtered and evaporated+co-evaporated with toluene The compound was purified by chromatography (0→10% EtOH in Methylene chloride)

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

実験手順: H2WO4 (0.029 g, 0.114 mmol) was stirred in H2O (10 ml). 50% NaOH (0.040 ml) was first added (pH>12) and then ACOH (0.040 ml) to reach pH 5. 4-methylsulfanyl-phenol (4 g, 0.029 mol) was added and the reaction mixture was heated to 65° C. 30% H2O2 in H2O (3 ml) was added in portions over 10 minutes. The reaction mixture was allowed to stir at room temperature for 1 h. 50% NaHSO3 was added to quench the reaction. Methylene chloride was added and the compound was washed with brine and purified by chromatography (0→10% EtOH in methylene chloride) to give 1.9 g of 4-methanesulfinyl-phenol (1) (42%) and 1.5 g of 4-methanesulfonyl-phenol (2) (30%). to quench the reaction the compound was washed with brine purified by chromatography (0→10% EtOH in methylene chloride)

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

実験手順: H2WO4 (0.029 g, 0.114 mmol) was stirred in H2O (10 ml). 50% NaOH (0.040 ml) was first added (pH>12) and then ACOH (0.040 ml) to reach pH 5. 4-methylsulfanyl-phenol (4 g, 0.029 mol) was added and the reaction mixture was heated to 65° C. 30% H2O2 in H2O (3 ml) was added in portions over 10 minutes. The reaction mixture was allowed to stir at room temperature for 1 h. 50% NaHSO3 was added to quench the reaction. Methylene chloride was added and the compound was washed with brine and purified by chromatography (0→10% EtOH in methylene chloride) to give 1.9 g of 4-methanesulfinyl-phenol (1) (42%) and 1.5 g of 4-methanesulfonyl-phenol (2) (30%). to quench the reaction the compound was washed with brine purified by chromatography (0→10% EtOH in methylene chloride)

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 4-methanesulfinyl-phenol (Combi-Blocks Inc, San Diego, Calif., USA; 14 mg, 0.089 mmol), 4-(4-chloro-pyrazolo[3,4-d]pyrimidin-1-yl)-piperidine-1-carboxylic acid tert-butyl ester (Intermediate 19; 30 mg, 0.089 mmol), and potassium carbonate (27 mg, 0.196 mmol) in dimethylformamide (1 mL) was heated in a microwave oven at 160° C. for 10 min. Saturated sodium carbonate solution was added to the reaction mixture, and the mixture was then filtered through a pad of silica gel to remove the precipitate. The silica gel pad was washed with methanol and the solvents were evaporated from the filtrate. The residue was purified by HPLC to give 4-[4-(4-methanesulfinyl-phenoxy)-pyrazolo[3,4-d]pyrimidin-1-yl]-piperidine-1-carboxylic acid tert-butyl ester (15 mg, 36%) as a white solid. Mass spectrum MH+=458. the mixture was then filtered through a pad of silica gel to remove the precipitate The silica gel pad was washed with methanol the solvents were evaporated from the filtrate The residue was purified by HPLC

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 4-methanesulfinyl-phenol (1.52 g, 9.7 mmol) in DMF (30 ml) cesium carbonate (4.2 g, 12.9 mmol) was added, followed by addition of 5-bromo-2-nitro pyridine (1.75 g, 8.6 mmol) and the mixture was stirred at 50° C. over night. The suspension was filtered and evaporated+co-evaporated with toluene. The compound was purified by chromatography (0→10% EtOH in Methylene chloride) to give 1.5 g (56%) of 5-(4-Methanesulfinyl-phenoxy)-2-nitro-pyridine. The suspension was filtered and evaporated+co-evaporated with toluene The compound was purified by chromatography (0→10% EtOH in Methylene chloride)

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

実験手順: H2WO4 (0.029 g, 0.114 mmol) was stirred in H2O (10 ml). 50% NaOH (0.040 ml) was first added (pH>12) and then ACOH (0.040 ml) to reach pH 5. 4-methylsulfanyl-phenol (4 g, 0.029 mol) was added and the reaction mixture was heated to 65° C. 30% H2O2 in H2O (3 ml) was added in portions over 10 minutes. The reaction mixture was allowed to stir at room temperature for 1 h. 50% NaHSO3 was added to quench the reaction. Methylene chloride was added and the compound was washed with brine and purified by chromatography (0→10% EtOH in methylene chloride) to give 1.9 g of 4-methanesulfinyl-phenol (1) (42%) and 1.5 g of 4-methanesulfonyl-phenol (2) (30%). to quench the reaction the compound was washed with brine purified by chromatography (0→10% EtOH in methylene chloride)

反応条件: temp:0.00; pressure:0.00; stir: