benzyl-(chloromethyl)-dimethylsilane

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

実験手順: To a solution of benzyldimethylsilylmethyl magnesium chloride, prepared from benzylchloromethyldimethyl silane (Fessenden, R. J., Coon, M. D., J. Med. Chem. Vol. 9 pp. 262-263 (1966)) (1.5 g, 7.55 mmol) and magnesium (0.19 g, 7.9 mmol) in diethyl ether (15 ml), is added paraformaldehyde (0.228 g, 7.6 mmol). Then the mixture is refluxed for 18 hours, cooled to 0° C. and hydrolyzed with 1N HCl (25 ml). The organic layer is washed with water brine and dried over MgSO4. The solution is filtered and solvent removed in vacuo. Chromatography (silica gel, hexane/diethyl ether 70/30) afforded β-(benzyldimethylsilyl)ethanol as an oil (0.84 g, 57% yield). Then the mixture is refluxed for 18 hours The organic layer is washed with water brine dried over MgSO4 The solution is filtered solvent removed in vacuo

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

実験手順: To a solution of benzyldimethylsilylmethyl magnesium chloride, prepared from benzylchloromethyldimethyl silane (Fessenden, R. J., Coon, M. D., J. Med. Chem. Vol. 9 pp. 262-263 (1966)) (1.5 g, 7.55 mmol) and magnesium (0.19 g, 7.9 mmol) in diethyl ether (15 ml), is added paraformaldehyde (0.228 g, 7.6 mmol). Then the mixture is refluxed for 18 hours, cooled to 0° C. and hydrolyzed with 1N HCl (25 ml). The organic layer is washed with water brine and dried over MgSO4. The solution is filtered and solvent removed in vacuo. Chromatography (silica gel, hexane/diethyl ether 70/30) afforded β-(benzyldimethylsilyl)ethanol as an oil (0.84 g, 57% yield). Then the mixture is refluxed for 18 hours The organic layer is washed with water brine dried over MgSO4 The solution is filtered solvent removed in vacuo

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 2 L 3-necked flask equipped with a nitrogen inlet, a 500 ml dropping funnel and a thermometer, was placed 500 ml of tetrahydrofuran. Chloro(chloromethyl)-dimethylsilane (100 ml, 0.744 mol) was added by syringe and the colorless solution cooled to 0° C. in an ice/acetone bath. Then benzylmagnesium chloride (2.0 M solution, 400 ml, 0.8 mol) was transferred to the dropping funnel by syringe and added dropwise over 2 hours. A slightly exothermic reaction was observed and the temperature was maintained below 10° C. After addition of the benzylmagnesium chloride was complete, the ice bath was allowed to warm up to room temperature without heating, and the reaction mixture was stirred overnight. Thereafter hexane (300 ml) was added and the reaction mixture was worked up by dropwise addition of saturated aqueous ammonium chloride (300 ml) and transferred to a 2 L separatory funnel with additional hexane (300 ml). After partitioning, the organic layer was washed with saturated aqueous ammonium chloride (200 ml) and saturated aqueous sodium chloride (200 ml). The combined aqueous layers were backwashed with hexane (2×500 ml). The combined organic layers were dried over magnesium sulfate, evaporated on a rotary evaporator, and finally evaporated with an oil pump to give a colorless oil 162.0 g (109.5% yield). A quantitative yield was assumed with a purity of the crude product as 91.3%. In a 2 L 3-necked flask equipped with a nitrogen inlet added dropwise over 2 hours A slightly exothermic reaction the temperature was maintained below 10° C to warm up to room temperature without heating After partitioning the organic layer was washed with saturated aqueous ammonium chloride (200 ml) and saturated aqueous sodium chloride (200 ml) The combined organic layers were dried over magnesium sulfate evaporated on a rotary evaporator finally evaporated with an oil pump

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 2 L 3-necked flask equipped with a nitrogen inlet, a 500 ml dropping funnel and a thermometer, was placed 500 ml of tetrahydrofuran. Chloro(chloromethyl)-dimethylsilane (100 ml, 0.744 mol) was added by syringe and the colorless solution cooled to 0° C. in an ice/acetone bath. Then benzylmagnesium chloride (2.0 M solution, 400 ml, 0.8 mol) was transferred to the dropping funnel by syringe and added dropwise over 2 hours. A slightly exothermic reaction was observed and the temperature was maintained below 10° C. After addition of the benzylmagnesium chloride was complete, the ice bath was allowed to warm up to room temperature without heating, and the reaction mixture was stirred overnight. Thereafter hexane (300 ml) was added and the reaction mixture was worked up by dropwise addition of saturated aqueous ammonium chloride (300 ml) and transferred to a 2 L separatory funnel with additional hexane (300 ml). After partitioning, the organic layer was washed with saturated aqueous ammonium chloride (200 ml) and saturated aqueous sodium chloride (200 ml). The combined aqueous layers were backwashed with hexane (2×500 ml). The combined organic layers were dried over magnesium sulfate, evaporated on a rotary evaporator, and finally evaporated with an oil pump to give a colorless oil 162.0 g (109.5% yield). A quantitative yield was assumed with a purity of the crude product as 91.3%. In a 2 L 3-necked flask equipped with a nitrogen inlet added dropwise over 2 hours A slightly exothermic reaction the temperature was maintained below 10° C to warm up to room temperature without heating After partitioning the organic layer was washed with saturated aqueous ammonium chloride (200 ml) and saturated aqueous sodium chloride (200 ml) The combined organic layers were dried over magnesium sulfate evaporated on a rotary evaporator finally evaporated with an oil pump

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

実験手順: To a solution of benzyldimethylsilylmethyl magnesium chloride, prepared from benzylchloromethyldimethyl silane (Fessenden, R. J., Coon, M. D., J. Med. Chem. Vol. 9 pp. 262-263 (1966)) (1.5 g, 7.55 mmol) and magnesium (0.19 g, 7.9 mmol) in diethyl ether (15 ml), is added paraformaldehyde (0.228 g, 7.6 mmol). Then the mixture is refluxed for 18 hours, cooled to 0° C. and hydrolyzed with 1N HCl (25 ml). The organic layer is washed with water brine and dried over MgSO4. The solution is filtered and solvent removed in vacuo. Chromatography (silica gel, hexane/diethyl ether 70/30) afforded β-(benzyldimethylsilyl)ethanol as an oil (0.84 g, 57% yield). Then the mixture is refluxed for 18 hours The organic layer is washed with water brine dried over MgSO4 The solution is filtered solvent removed in vacuo

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

実験手順: To a solution of benzyldimethylsilylmethyl magnesium chloride, prepared from benzylchloromethyldimethyl silane (Fessenden, R. J., Coon, M. D., J. Med. Chem. Vol. 9 pp. 262-263 (1966)) (1.5 g, 7.55 mmol) and magnesium (0.19 g, 7.9 mmol) in diethyl ether (15 ml), is added paraformaldehyde (0.228 g, 7.6 mmol). Then the mixture is refluxed for 18 hours, cooled to 0° C. and hydrolyzed with 1N HCl (25 ml). The organic layer is washed with water brine and dried over MgSO4. The solution is filtered and solvent removed invacuo. Chromatography (silica gel, hexane/diethyl ether 70/30) afforded β-(benzyldimethylsilyl)ethanol as an oil (0.84 g, 57% yield). m.p. 132°-133° C. Then the mixture is refluxed for 18 hours The organic layer is washed with water brine dried over MgSO4 The solution is filtered solvent removed invacuo

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

実験手順: 9.9 g of chloromethyl-benzyl-dimethylsilane and 8.9 g of pyrrolidine are refluxed in 40 ml of xylene for 6 hours, then the reaction mixture is washed 5 times with a total of 250 ml of water at room temperature. The organic phase is dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated to solvent-free. The slightly yellow oily residue is dissolved in 20 ml of ethyl acetate and the solution is acidified to pH 4.5 by adding ethanolic hydrogen chloride solution. After drying the precipitate the named product is obtained in a yield of 11.3 g (94%), m.p.: 140°14 140.5° C. the reaction mixture is washed 5 times with a total of 250 ml of water at room temperature The organic phase is dried over anhydrous magnesium sulfate filtered the filtrate is evaporated to solvent-free The slightly yellow oily residue is dissolved in 20 ml of ethyl acetate by adding ethanolic hydrogen chloride solution After drying the precipitate the named product is obtained in a yield of 11.3 g (94%) 140°14 140.5° C.

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

実験手順: To a solution of benzyldimethylsilylmethyl magnesium chloride, prepared from benzylchloromethyldimethyl silane (Fessenden, R. J., Coon, M. D., J. Med. Chem. Vol. 9 pp. 262-263 (1966)) (1.5 g, 7.55 mmol) and magnesium (0.19 g, 7.9 mmol) in diethyl ether (15 ml), is added paraformaldehyde (0.228 g, 7.6 mmol). Then the mixture is refluxed for 18 hours, cooled to 0° C. and hydrolyzed with 1N HCl (25 ml). The organic layer is washed with water brine and dried over MgSO4. The solution is filtered and solvent removed inuacuo. Chromatography (silica gel, hexane/diethyl ether 70/30) afforded β-(benzyldimethylsilyl)ethanol as an oil (0.84 g, 57% yield). Then the mixture is refluxed for 18 hours The organic layer is washed with water brine dried over MgSO4 The solution is filtered solvent removed inuacuo

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

実験手順: 9.9 g of chloromethyl-benzyl-dimethylsilane and 8.9 g of pyrrolidine are refluxed in 40 ml of xylene for 6 hours, then the reaction mixture is washed 5 times with a total of 250 ml of water at room temperature. The organic phase is dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated to solvent-free. The slightly yellow oily residue is dissolved in 20 ml of ethyl acetate and the solution is acidified to pH 4.5 by adding ethanolic hydrogen chloride solution. After drying the precipitate the named product is obtained in a yield of 11.3 g (94%), m.p.: 140°-140.5° C. the reaction mixture is washed 5 times with a total of 250 ml of water at room temperature The organic phase is dried over anhydrous magnesium sulfate filtered the filtrate is evaporated to solvent-free The slightly yellow oily residue is dissolved in 20 ml of ethyl acetate by adding ethanolic hydrogen chloride solution After drying the precipitate the named product is obtained in a yield of 11.3 g (94%), m.p.: 140°-140.5° C.

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 2 L 3-necked flask equipped with a nitrogen inlet, a 500 ml dropping funnel and a thermometer, was placed 500 ml of tetrahydrofuran. Chloro(chloromethyl)-dimethylsilane (100 ml, 0.744 mol) was added by syringe and the colorless solution cooled to 0° C. in an ice/acetone bath. Then benzylmagnesium chloride (2.0 M solution, 400 ml, 0.8 mol) was transferred to the dropping funnel by syringe and added dropwise over 2 hours. A slightly exothermic reaction was observed and the temperature was maintained below 10° C. After addition of the benzylmagnesium chloride was complete, the ice bath was allowed to warm up to room temperature without heating, and the reaction mixture was stirred overnight. Thereafter hexane (300 ml) was added and the reaction mixture was worked up by dropwise addition of saturated aqueous ammonium chloride (300 ml) and transferred to a 2 L separatory funnel with additional hexane (300 ml). After partitioning, the organic layer was washed with saturated aqueous ammonium chloride (200 ml) and saturated aqueous sodium chloride (200 ml). The combined aqueous layers were backwashed with hexane (2×500 ml). The combined organic layers were dried over magnesium sulfate, evaporated on a rotary evaporator, and finally evaporated with an oil pump to give a colorless oil 162.0 g (109.5% yield). A quantitative yield was assumed with a purity of the crude product as 91.3%. In a 2 L 3-necked flask equipped with a nitrogen inlet added dropwise over 2 hours A slightly exothermic reaction the temperature was maintained below 10° C to warm up to room temperature without heating After partitioning the organic layer was washed with saturated aqueous ammonium chloride (200 ml) and saturated aqueous sodium chloride (200 ml) The combined organic layers were dried over magnesium sulfate evaporated on a rotary evaporator finally evaporated with an oil pump

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 2 L 3-necked flask equipped with a nitrogen inlet, a 500 ml dropping funnel and a thermometer, was placed 500 ml of tetrahydrofuran. Chloro(chloromethyl)-dimethylsilane (100 ml, 0.744 mol) was added by syringe and the colorless solution cooled to 0° C. in an ice/acetone bath. Then benzylmagnesium chloride (2.0 M solution, 400 ml, 0.8 mol) was transferred to the dropping funnel by syringe and added dropwise over 2 hours. A slightly exothermic reaction was observed and the temperature was maintained below 10° C. After addition of the benzylmagnesium chloride was complete, the ice bath was allowed to warm up to room temperature without heating, and the reaction mixture was stirred overnight. Thereafter hexane (300 ml) was added and the reaction mixture was worked up by dropwise addition of saturated aqueous ammonium chloride (300 ml) and transferred to a 2 L separatory funnel with additional hexane (300 ml). After partitioning, the organic layer was washed with saturated aqueous ammonium chloride (200 ml) and saturated aqueous sodium chloride (200 ml). The combined aqueous layers were backwashed with hexane (2×500 ml). The combined organic layers were dried over magnesium sulfate, evaporated on a rotary evaporator, and finally evaporated with an oil pump to give a colorless oil 162.0 g (109.5% yield). A quantitative yield was assumed with a purity of the crude product as 91.3%. In a 2 L 3-necked flask equipped with a nitrogen inlet added dropwise over 2 hours A slightly exothermic reaction the temperature was maintained below 10° C to warm up to room temperature without heating After partitioning the organic layer was washed with saturated aqueous ammonium chloride (200 ml) and saturated aqueous sodium chloride (200 ml) The combined organic layers were dried over magnesium sulfate evaporated on a rotary evaporator finally evaporated with an oil pump

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

実験手順: To a solution of benzyldimethylsilylmethyl magnesium chloride, prepared from benzylchloromethyldimethyl silane (Fessenden, R. J., Coon, M. D., J. Med. Chem. Vol. 9 pp. 262-263 (1966)) (1.5 g, 7.55 mmol) and magnesium (0.19 g, 7.9 mmol) in diethyl ether (15 ml), is added paraformaldehyde (0.228 g, 7.6 mmol). Then the mixture is refluxed for 18 hours, cooled to 0° C. and hydrolyzed with 1N HCl (25 ml). The organic layer is washed with water brine and dried over MgSO4. The solution is filtered and solvent removed in vacuo. Chromatography (silica gel, hexane/diethyl ether 70/30) afforded β-(benzyldimethylsilyl)ethanol as an oil (0.84 g, 57% yield). Then the mixture is refluxed for 18 hours The organic layer is washed with water brine dried over MgSO4 The solution is filtered solvent removed in vacuo