[chlorosulfonyloxy(dimethyl)silyl]methane

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

実験手順: In a first step, a film of 100 cm2 with a thickness of 100 μm, dried beforehand at 110° C. under vacuum (10 mbar), was immersed in 200 ml of dichloroethane (DCE) and the whole mixture is brought to 60° C. In parallel, an anhydrous solution of trimethylsilyl chlorosulfonate was prepared by dissolving 47.2 g (0.434 moles) of trimethylsilane chloride and 42.2 g (0.36 moles) of ClSO3H, both the constituents being anhydrous, in 50 ml of dry DCE with magnetic stirring and under argon, for a duration of 30 minutes, with HCl formed being trapped. In a first step, a film of 100 cm2 with a thickness of 100 μm, dried beforehand at 110° C. under vacuum (10 mbar) is brought to 60° C formed

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

実験手順: To 2 ml of absolute pyridine in 20 ml of dry dichloromethane is added trimethylsilyloxysulfonyl chloride (3.7 ml) in 5 ml of dry dichloromethane. The addition is accomplished at -30° C., under nitrogen, over a 10 minute period. After stirring at ambient temperature for 30 minutes, the flask is evacuated to yield a pyridine-sulfur trioxide complex. (trans)-3-t-Butoxycarbonylamino-4-ethyl-2-azetidinone (2.67 g) and 20 ml of dry pyridine are added to the flask which is then placed in an oil bath preheated to 90° C. After 15 minutes a clear solution is obtained and poured into 200 ml of a 1M solution of dibasic potassium phosphate. After the addition of 27 g of dibasic potassium phosphate and 100 ml of water a clear solution is obtained. The solution is extracted with two 60 ml portions of ethyl acetate. Tetrabutylammonium hydrogensulfate is added to the aqueous layer, and the aqueous solution is extracted with three 100 ml portions of dichloromethane and the combined organic layers are dried over MgSO4. Concentration in vacuo yields 6.9 g of the title compound. The addition the flask is evacuated to yield a pyridine-sulfur trioxide complex is then placed in an oil bath preheated to 90° C After 15 minutes a clear solution is obtained is obtained The solution is extracted with two 60 ml portions of ethyl acetate Tetrabutylammonium hydrogensulfate is added to the aqueous layer the aqueous solution is extracted with three 100 ml portions of dichloromethane the combined organic layers are dried over MgSO4 Concentration in vacuo

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

実験手順: To 2 ml of absolute pyridine in 20 ml of dry dichloromethane is added trimethylsilyloxysulfonyl chloride (3.7 ml) in 5 ml of dry dichloromethane. The addition is accomplished at -30° C., under nitrogen, over a 10 minute period. After stirring at ambient temperature for 30 minutes, the flask is evacuated to yield a pyridine-sulfur trioxide complex. (trans)-3-t-Butoxycarbonylamino-4-ethyl-2-azetidinone (2.67 g) and 20 ml of dry pyridine are added to the flask which is then placed in an oil bath preheated to 90° C. After 15 minutes a clear solution is obtained and poured into 200 ml of a 1M solution of dibasic potassium phosphate. After the addition of 27 g of dibasic potassium phosphate and 100 ml of water a clear solution is obtained. The solution is extracted with two 60 ml portions of ethyl acetate. Tetrabutylammonium hydrogensulfate is added to the aqueous layer, and the aqueous solution is extracted with three 100 ml portions of dichloromethane and the combined organic layers are dried over MgSO4. Concentration in vacuo yields 6.9 g of the title compound. The addition the flask is evacuated to yield a pyridine-sulfur trioxide complex is then placed in an oil bath preheated to 90° C After 15 minutes a clear solution is obtained is obtained The solution is extracted with two 60 ml portions of ethyl acetate Tetrabutylammonium hydrogensulfate is added to the aqueous layer the aqueous solution is extracted with three 100 ml portions of dichloromethane the combined organic layers are dried over MgSO4 Concentration in vacuo

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

実験手順: To 2 ml of absolute pyridine in 20 ml of dry dichloromethane is added trimethylsilyloxysulfonyl chloride (3.7 ml) in 5 ml of dry dichloromethane. The addition is accomplished at -30° C., under nitrogen, over a 10 minute period. After stirring at ambient temperature for 30 minutes, the flask is evacuated to yield a pyridine-sulfur trioxide complex. (trans)-3-t-Butoxycarbonylamino-4-ethyl-2-azetidinone (2.67 g) and 20 ml of dry pyridine are added to the flask which is then placed in an oil bath preheated to 90° C. After 15 minutes a clear solution is obtained and poured into 200 ml of a 1M solution of dibasic potassium phosphate. After the addition of 27 g of dibasic potassium phosphate and 100 ml of water a clear solution is obtained. The solution is extracted with two 60 ml portions of ethyl acetate. Tetrabutylammonium hydrogensulfate is added to the aqueous layer, and the aqueous solution is extracted with three 100 ml portions of dichloromethane and the combined organic layers are dried over MgSO4. Concentration in vacuo yields 6.9 g of the title compound. The addition the flask is evacuated to yield a pyridine-sulfur trioxide complex is then placed in an oil bath preheated to 90° C After 15 minutes a clear solution is obtained is obtained The solution is extracted with two 60 ml portions of ethyl acetate Tetrabutylammonium hydrogensulfate is added to the aqueous layer the aqueous solution is extracted with three 100 ml portions of dichloromethane the combined organic layers are dried over MgSO4 Concentration in vacuo

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

実験手順: Under an argon gas atmosphere, a solution of 9.44 g (50 mmol) of trimethylsilyl chlorosulfonate in 50 ml of carbon tetrachloride was gradually added under stirring to a solution of 18.5 g (50 mmol) of 1-methyl-2-tri-n-butylstannylpyrrole in 150 ml of carbon tetrachloride, followed by stirring at 50° C. for 30 minutes and further at room temperature for 30 minutes. To the reaction mixture, 300 ml of a saturated aqueous solution of sodium hydrogencarbonate were added, followed by stirring at room temperature for 20 minutes. The reaction mixture was allowed to separate into two layers. The water layer was collected and then washed with ethyl ether (100 ml×3 times). From the water layer, water was distilled off under reduced pressure, followed by the addition of ethanol to the residue. The resulting mixture was boiled and then subjected to hot filtration. The solvent in the filtrate was distilled off under reduced pressure, and the thus-obtained solid was washed with n-pentane (200 ml×2 times) and then dried under reduced pressure. Colorless powdery crystals (6.67 g) were obtained. by stirring at room temperature for 20 minutes to separate into two layers The water layer was collected washed with ethyl ether (100 ml×3 times) From the water layer, water was distilled off under reduced pressure followed by the addition of ethanol to the residue subjected to hot filtration The solvent in the filtrate was distilled off under reduced pressure the thus-obtained solid was washed with n-pentane (200 ml×2 times) dried under reduced pressure

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

実験手順: In a first step, a film of 100 cm2 with a thickness of 100 μm, dried beforehand at 110° C. under vacuum (10 mbar), was immersed in 200 ml of dichloroethane (DCE) and the whole mixture is brought to 60° C. In parallel, an anhydrous solution of trimethylsilyl chlorosulfonate was prepared by dissolving 47.2 g (0.434 moles) of trimethylsilane chloride and 42.2 g (0.36 moles) of ClSO3H, both the constituents being anhydrous, in 50 ml of dry DCE with magnetic stirring and under argon, for a duration of 30 minutes, with HCl formed being trapped. In a first step, a film of 100 cm2 with a thickness of 100 μm, dried beforehand at 110° C. under vacuum (10 mbar) is brought to 60° C formed

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

実験手順: To 2 ml of absolute pyridine in 20 ml of dry dichloromethane is added trimethylsilyloxysulfonyl chloride (3.7 ml) in 5 ml of dry dichloromethane. The addition is accomplished at -30° C., under nitrogen, over a 10 minute period. After stirring at ambient temperature for 30 minutes, the flask is evacuated to yield a pyridine-sulfur trioxide complex. (trans)-3-t-Butoxycarbonylamino-4-ethyl-2-azetidinone (2.67 g) and 20 ml of dry pyridine are added to the flask which is then placed in an oil bath preheated to 90° C. After 15 minutes a clear solution is obtained and poured into 200 ml of a 1M solution of dibasic potassium phosphate. After the addition of 27 g of dibasic potassium phosphate and 100 ml of water a clear solution is obtained. The solution is extracted with two 60 ml portions of ethyl acetate. Tetrabutylammonium hydrogensulfate is added to the aqueous layer, and the aqueous solution is extracted with three 100 ml portions of dichloromethane and the combined organic layers are dried over MgSO4. Concentration in vacuo yields 6.9 g of the title compound. The addition the flask is evacuated to yield a pyridine-sulfur trioxide complex is then placed in an oil bath preheated to 90° C After 15 minutes a clear solution is obtained is obtained The solution is extracted with two 60 ml portions of ethyl acetate Tetrabutylammonium hydrogensulfate is added to the aqueous layer the aqueous solution is extracted with three 100 ml portions of dichloromethane the combined organic layers are dried over MgSO4 Concentration in vacuo

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

実験手順: 1-(4,5-Dihydro-1H-imidazol-2-ylmethyl)-1H-indole (1.0 g, 4.243 mmol) was dissolved/suspended in dichloroethane (120 ml) and cooled in ice under a nitrogen atmosphere. Trimethylsilylchlorosulfonate (0.654 ml, 0.801 g, 4.243 mmol) was added to the cooled solution dropwise with stirring. The mixture was allowed to warm up to room temperature with stirring, and stirring was continued overnight. Methanol (20 mL) was then added, followed by stirring at room temperature for 20 minutes. The mixture was then rotovapped to dryness. The crude product was recrystallized from MeOH/EtOAc as the hydrochloride salt of 1-(4,5-dihydro-1H-imidazol-2-ylmethyl)-1H-indole-3-sulfonic acid. cooled in ice under a nitrogen atmosphere with stirring stirring by stirring at room temperature for 20 minutes The crude product was recrystallized from MeOH/EtOAc as the hydrochloride salt of 1-(4,5-dihydro-1H-imidazol-2-ylmethyl)-1H-indole-3-sulfonic acid

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 7-Chloroindole (1.51 g, 10 mmole) was dissolved in 2 ml dichloroethane and cooled under nitrogen to −10° C. in an ice-salt-acetone bath. Trimethylsilylchlorosulfonate (1.89 g, 1.6 ml, 10 mmole) was slowly added with stirring. Upon termination of the addition, the reaction was allowed to warm to room temperature and stirred for 30 min at this temperature. The dark red solution was evaporated to dryness and the solvent was replaced with 50 ml ethyl acetate. Methanol (5 ml) was added and the solvents were removed and the residue thoroughly dried to afford the crude 5-chloro-1H-indole-3-sulfonic acid as a red oil. Step 2 7-Chloro-1H-indole-3-sulfonic acid dimethylamide Upon termination of the addition to warm to room temperature stirred for 30 min at this temperature The dark red solution was evaporated to dryness Methanol (5 ml) was added the solvents were removed the residue thoroughly dried

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

実験手順: 1-(4,5-Dihydro-1H-imidazol-2-ylmethyl)-1H-indole (1.0 g, 4.243 mmol) was dissolved/suspended in dichloroethane (120 ml) and cooled in ice under a nitrogen atmosphere. Trimethylsilylchlorosulfonate (0.654 ml, 0.801 g, 4.243 mmol) was added to the cooled solution dropwise with stirring. The mixture was allowed to warm up to room temperature with stirring, and stirring was continued overnight. Methanol (20 mL) was then added, followed by stirring at room temperature for 20 minutes. The mixture was then rotovapped to dryness. The crude product was recrystallized from MeOH/EtOAc as the hydrochloride salt of 1-(4,5-dihydro-1H-imidazol-2-ylmethyl)-1H-indole-3-sulfonic acid. cooled in ice under a nitrogen atmosphere with stirring stirring by stirring at room temperature for 20 minutes The crude product was recrystallized from MeOH/EtOAc as the hydrochloride salt of 1-(4,5-dihydro-1H-imidazol-2-ylmethyl)-1H-indole-3-sulfonic acid

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 7-Chloroindole (1.51 g, 10 mmole) was dissolved in 2 ml dichloroethane and cooled under nitrogen to −10° C. in an ice-salt-acetone bath. Trimethylsilylchlorosulfonate (1.89 g, 1.6 ml, 10 mmole) was slowly added with stirring. Upon termination of the addition, the reaction was allowed to warm to room temperature and stirred for 30 min at this temperature. The dark red solution was evaporated to dryness and the solvent was replaced with 50 ml ethyl acetate. Methanol (5 ml) was added and the solvents were removed and the residue thoroughly dried to afford the crude 5-chloro-1H-indole-3-sulfonic acid as a red oil. Step 2 7-Chloro-1H-indole-3-sulfonic acid dimethylamide Upon termination of the addition to warm to room temperature stirred for 30 min at this temperature The dark red solution was evaporated to dryness Methanol (5 ml) was added the solvents were removed the residue thoroughly dried

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

実験手順: Under an argon gas atmosphere, a solution of 9.44 g (50 mmol) of trimethylsilyl chlorosulfonate in 50 ml of carbon tetrachloride was gradually added under stirring to a solution of 18.5 g (50 mmol) of 1-methyl-2-tri-n-butylstannylpyrrole in 150 ml of carbon tetrachloride, followed by stirring at 50° C. for 30 minutes and further at room temperature for 30 minutes. To the reaction mixture, 300 ml of a saturated aqueous solution of sodium hydrogencarbonate were added, followed by stirring at room temperature for 20 minutes. The reaction mixture was allowed to separate into two layers. The water layer was collected and then washed with ethyl ether (100 ml×3 times). From the water layer, water was distilled off under reduced pressure, followed by the addition of ethanol to the residue. The resulting mixture was boiled and then subjected to hot filtration. The solvent in the filtrate was distilled off under reduced pressure, and the thus-obtained solid was washed with n-pentane (200 ml×2 times) and then dried under reduced pressure. Colorless powdery crystals (6.67 g) were obtained. by stirring at room temperature for 20 minutes to separate into two layers The water layer was collected washed with ethyl ether (100 ml×3 times) From the water layer, water was distilled off under reduced pressure followed by the addition of ethanol to the residue subjected to hot filtration The solvent in the filtrate was distilled off under reduced pressure the thus-obtained solid was washed with n-pentane (200 ml×2 times) dried under reduced pressure