N-sulfinylmethanesulfonamide

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 51.6 g (0.365 mole) of N-sulphinylmethanesulphonamide in 50 ml of benzene are added to a solution of 60 g (0.298 mole) of methyl 3-sulphinylamino-4-methylbenzoate in 200 ml of benzene at room temperature under argon. Thereafter, 24.9 g (0.315 mole) of pyridine, dissolved in 75 ml of benzene, are added in portions to the reaction mixture, while cooling with ice. The mixture is subsequently stirred at 0° C. for 10 minutes and then heated under reflux for 45 hours. After cooling, the benzene and pyridine are distilled off in vacuo, the oil which remains is poured into 150 ml of water and the mixture is acidified to pH 4 with 2N HCl. A brown solid thereby forms from the oil, and is extracted with chloroform. The chloroform extracts are washed with water, dried over MgSO4 and concentrated to dryness. The oil which remains crystallizes to a brown-yellow material by adding n-hexane, and the material is filtered off with suction and washed with n-hexane. are added in portions to the reaction mixture while cooling with ice heated under reflux for 45 hours After cooling the benzene and pyridine are distilled off in vacuo the oil which remains is poured into 150 ml of water A brown solid thereby forms from the oil, and is extracted with chloroform The chloroform extracts are washed with water dried over MgSO4 concentrated to dryness The oil which remains crystallizes to a brown-yellow material by adding n-hexane the material is filtered off with suction washed with n-hexane

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of o-toluidine (10 g, 93.4 mmol) in 50 mL toluene was added SOCl2 (12.1 g, 102 mmol) dropwise at 0° C. After the addition was complete, the reaction mixture was heated to reflux and stirred overnight. The reaction mixture was cooled to room temperature, and concentrated under reduced pressure to give a yellow oil. The oil was dissolved in toluene (100 mL), then a solution of N-sulfinylmethanesulfonamide (20.6 g, 146 mmol) was added dropwise, followed by pyridine (7.3 g, 93.4 mmol). The mixture was heated to reflux and stirred at that temperature overnight. Toluene was then removed under reduced pressure, the residue was dissolved in EtOAc (200 mL) and washed with water (2×200 mL). The organic layer was washed with brine, dried and evaporated to give the crude product. The crude product was purified by column chromatography (3% EtOAc/PE) to afford 6.2 g title compound as colorless oil. 1H NMR (CHLOROFORM-d) δ 9.22 (s, 1H), 7.88 (d, J=9.7 Hz, 1H), 7.80 (d, J=8.6 Hz, 1H), 7.46 (ddd, J=8.9, 6.5, 1.2 Hz, 1H), 7.26 (dd, J=7.9, 6.6 Hz, 1H). After the addition the reaction mixture was heated to reflux concentrated under reduced pressure to give a yellow oil The mixture was heated to reflux stirred at that temperature overnight Toluene was then removed under reduced pressure the residue was dissolved in EtOAc (200 mL) washed with water (2×200 mL) The organic layer was washed with brine dried evaporated to give the crude product The crude product was purified by column chromatography (3% EtOAc/PE)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of o-toluidine (10 g, 93.4 mmol) in 50 mL toluene was added SOCl2 (12.1 g, 102 mmol) dropwise at 0° C. After the addition was complete, the reaction mixture was heated to reflux and stirred overnight. The reaction mixture was cooled to room temperature, and concentrated under reduced pressure to give a yellow oil. The oil was dissolved in toluene (100 mL), then a solution of N-sulfinylmethanesulfonamide (20.6 g, 146 mmol) was added dropwise, followed by pyridine (7.3 g, 93.4 mmol). The mixture was heated to reflux and stirred at that temperature overnight. Toluene was then removed under reduced pressure, the residue was dissolved in EtOAc (200 mL) and washed with water (2×200 mL). The organic layer was washed with brine, dried and evaporated to give the crude product. The crude product was purified by column chromatography (3% EtOAc/PE) to afford 6.2 g title compound as colorless oil. 1H NMR (CHLOROFORM-d) δ 9.22 (s, 1H), 7.88 (d, J=9.7 Hz, 1H), 7.80 (d, J=8.6 Hz, 1H), 7.46 (ddd, J=8.9, 6.5, 1.2 Hz, 1H), 7.26 (dd, J=7.9, 6.6 Hz, 1H). After the addition the reaction mixture was heated to reflux concentrated under reduced pressure to give a yellow oil The mixture was heated to reflux stirred at that temperature overnight Toluene was then removed under reduced pressure the residue was dissolved in EtOAc (200 mL) washed with water (2×200 mL) The organic layer was washed with brine dried evaporated to give the crude product The crude product was purified by column chromatography (3% EtOAc/PE)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of o-toluidine (10 g, 93.4 mmol) in 50 mL toluene was added SOCl2 (12.1 g, 102 mmol) dropwise at 0° C. After the addition was complete, the reaction mixture was heated to reflux and stirred overnight. The reaction mixture was cooled to room temperature, and concentrated under reduced pressure to give a yellow oil. The oil was dissolved in toluene (100 mL), then a solution of N-sulfinylmethanesulfonamide (20.6 g, 146 mmol) was added dropwise, followed by pyridine (7.3 g, 93.4 mmol). The mixture was heated to reflux and stirred at that temperature overnight. Toluene was then removed under reduced pressure, the residue was dissolved in EtOAc (200 mL) and washed with water (2×200 mL). The organic layer was washed with brine, dried and evaporated to give the crude product. The crude product was purified by column chromatography (3% EtOAc/PE) to afford 6.2 g title compound as colorless oil. 1H NMR (CHLOROFORM-d) δ 9.22 (s, 1H), 7.88 (d, J=9.7 Hz, 1H), 7.80 (d, J=8.6 Hz, 1H), 7.46 (ddd, J=8.9, 6.5, 1.2 Hz, 1H), 7.26 (dd, J=7.9, 6.6 Hz, 1H). After the addition the reaction mixture was heated to reflux concentrated under reduced pressure to give a yellow oil The mixture was heated to reflux stirred at that temperature overnight Toluene was then removed under reduced pressure the residue was dissolved in EtOAc (200 mL) washed with water (2×200 mL) The organic layer was washed with brine dried evaporated to give the crude product The crude product was purified by column chromatography (3% EtOAc/PE)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of o-toluidine (10 g, 93.4 mmol) in 50 mL toluene was added SOCl2 (12.1 g, 102 mmol) dropwise at 0° C. After the addition was complete, the reaction mixture was heated to reflux and stirred overnight. The reaction mixture was cooled to room temperature, and concentrated under reduced pressure to give a yellow oil. The oil was dissolved in toluene (100 mL), then a solution of N-sulfinylmethanesulfonamide (20.6 g, 146 mmol) was added dropwise, followed by pyridine (7.3 g, 93.4 mmol). The mixture was heated to reflux and stirred at that temperature overnight. Toluene was then removed under reduced pressure, the residue was dissolved in EtOAc (200 mL) and washed with water (2×200 mL). The organic layer was washed with brine, dried and evaporated to give the crude product. The crude product was purified by column chromatography (3% EtOAc/PE) to afford 6.2 g title compound as colorless oil. 1H NMR (CHLOROFORM-d) δ 9.22 (s, 1H), 7.88 (d, J=9.7 Hz, 1H), 7.80 (d, J=8.6 Hz, 1H), 7.46 (ddd, J=8.9, 6.5, 1.2 Hz, 1H), 7.26 (dd, J=7.9, 6.6 Hz, 1H). After the addition the reaction mixture was heated to reflux concentrated under reduced pressure to give a yellow oil The mixture was heated to reflux stirred at that temperature overnight Toluene was then removed under reduced pressure the residue was dissolved in EtOAc (200 mL) washed with water (2×200 mL) The organic layer was washed with brine dried evaporated to give the crude product The crude product was purified by column chromatography (3% EtOAc/PE)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of methyl 2-methyl-3-(sulfinylamino)benzoate (15.0 g, 71.0 mmol) in benzene (200 mL) was added a solution of N-sulfinylmethanesulfonamide (10.0 g, 71.0 mmol) and pyridine (9.19 mL, 114 mmol) in benzene (80 mL) at 0° C. The reaction mixture was heated under reflux for 18 hr, water was added, and the mixture was extracted with dichloromethane. The extract was washed with saturated brine, and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane=20/80) to give the title compound (5.0 g, yield 36%). The reaction mixture was heated under reflux for 18 hr the mixture was extracted with dichloromethane The extract was washed with saturated brine dried over anhydrous sodium sulfate the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography (ethyl acetate/hexane=20/80)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 51.6 g (0.365 mole) of N-sulphinylmethanesulphonamide in 50 ml of benzene are added to a solution of 60 g (0.298 mole) of methyl 3-sulphinylamino-4-methylbenzoate in 200 ml of benzene at room temperature under argon. Thereafter, 24.9 g (0.315 mole) of pyridine, dissolved in 75 ml of benzene, are added in portions to the reaction mixture, while cooling with ice. The mixture is subsequently stirred at 0° C. for 10 minutes and then heated under reflux for 45 hours. After cooling, the benzene and pyridine are distilled off in vacuo, the oil which remains is poured into 150 ml of water and the mixture is acidified to pH 4 with 2N HCl. A brown solid thereby forms from the oil, and is extracted with chloroform. The chloroform extracts are washed with water, dried over MgSO4 and concentrated to dryness. The oil which remains crystallizes to a brown-yellow material by adding n-hexane, and the material is filtered off with suction and washed with n-hexane. are added in portions to the reaction mixture while cooling with ice heated under reflux for 45 hours After cooling the benzene and pyridine are distilled off in vacuo the oil which remains is poured into 150 ml of water A brown solid thereby forms from the oil, and is extracted with chloroform The chloroform extracts are washed with water dried over MgSO4 concentrated to dryness The oil which remains crystallizes to a brown-yellow material by adding n-hexane the material is filtered off with suction washed with n-hexane

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of o-toluidine (10 g, 93.4 mmol) in 50 mL toluene was added SOCl2 (12.1 g, 102 mmol) dropwise at 0° C. After the addition was complete, the reaction mixture was heated to reflux and stirred overnight. The reaction mixture was cooled to room temperature, and concentrated under reduced pressure to give a yellow oil. The oil was dissolved in toluene (100 mL), then a solution of N-sulfinylmethanesulfonamide (20.6 g, 146 mmol) was added dropwise, followed by pyridine (7.3 g, 93.4 mmol). The mixture was heated to reflux and stirred at that temperature overnight. Toluene was then removed under reduced pressure, the residue was dissolved in EtOAc (200 mL) and washed with water (2×200 mL). The organic layer was washed with brine, dried and evaporated to give the crude product. The crude product was purified by column chromatography (3% EtOAc/PE) to afford 6.2 g title compound as colorless oil. 1H NMR (CHLOROFORM-d) δ 9.22 (s, 1H), 7.88 (d, J=9.7 Hz, 1H), 7.80 (d, J=8.6 Hz, 1H), 7.46 (ddd, J=8.9, 6.5, 1.2 Hz, 1H), 7.26 (dd, J=7.9, 6.6 Hz, 1H). After the addition the reaction mixture was heated to reflux concentrated under reduced pressure to give a yellow oil The mixture was heated to reflux stirred at that temperature overnight Toluene was then removed under reduced pressure the residue was dissolved in EtOAc (200 mL) washed with water (2×200 mL) The organic layer was washed with brine dried evaporated to give the crude product The crude product was purified by column chromatography (3% EtOAc/PE)