chloro-methyl-diphenylsilane

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

実験手順: To a solution of lithium wire (2.08 g, 300 mmol) in dry tetrahydrofuran (150 ml) was added methyldiphenylsilyl chloride (15.8 ml, 75 mmol) and a catalytic amount of iodine. The reaction mixture was sonicated for 40 min and then stirred overnight at room temperature. The reaction mixture was cooled to −78° C. and 1,1-difluoroethylene (approx. 225 mmol) was passed through the mixture for 30 min. The mixture was stirred at −78° C. for 2 h and then warmed to room temperature. The reaction mixture was sonicated for 40 min The reaction mixture was cooled to −78° C. The mixture was stirred at −78° C. for 2 h warmed to room temperature

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

実験手順: To a solution of lithium wire (2.08 g, 300 mmol) in dry tetrahydrofuran (150 ml) was added methyldiphenylsilyl chloride (15.8 ml, 75 mmol) and a catalytic amount of iodine. The reaction mixture was sonicated for 40 min and then stirred overnight at room temperature. The reaction mixture was cooled to −78° C. and 1,1-difluoroethylene (approx. 225 mmol) was passed through the mixture for 30 min. The mixture was stirred at −78° C. for 2 h and then warmed to room temperature. The reaction mixture was quenched with saturated ammonium chloride solution and extracted with cyclohexane (×2). The combined extracts were washed with brine, dried (MgSO4) and concentrated in vacuo. The residue was purified by column chromatography (silica, 1 kg) eluting with hexane, followed by cyclohexane. The appropriate fractions were combined and concentrated to give Preparation 83 (7 g) as a colourless oil. The reaction mixture was sonicated for 40 min The reaction mixture was cooled to −78° C. The mixture was stirred at −78° C. for 2 h warmed to room temperature The reaction mixture was quenched with saturated ammonium chloride solution extracted with cyclohexane (×2) The combined extracts were washed with brine dried (MgSO4) concentrated in vacuo The residue was purified by column chromatography (silica, 1 kg) eluting with hexane concentrated to give

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

実験手順: To a solution of lithium wire (2.08 g, 300 mmol) in dry tetrahydrofuran (150 ml) was added methyldiphenylsilyl chloride (15.8 ml, 75 mmol) and a catalytic amount of iodine. The reaction mixture was sonicated for 40 min and then stirred overnight at room temperature. The reaction mixture was cooled to −78° C. and 1,1-difluoroethylene (approx. 225 mmol) was passed through the mixture for 30 min. The mixture was stirred at −78° C. for 2 h and then warmed to room temperature. The reaction mixture was quenched with saturated ammonium chloride solution and extracted with cyclohexane (×2). The combined extracts were washed with brine, dried (MgSO4) and concentrated in vacuo. The residue was purified by column chromatography (silica, 1 kg) eluting with hexane, followed by cyclohexane. The appropriate fractions were combined and concentrated to give Preparation 83 (7 g) as a colourless oil. The reaction mixture was sonicated for 40 min The reaction mixture was cooled to −78° C. The mixture was stirred at −78° C. for 2 h warmed to room temperature The reaction mixture was quenched with saturated ammonium chloride solution extracted with cyclohexane (×2) The combined extracts were washed with brine dried (MgSO4) concentrated in vacuo The residue was purified by column chromatography (silica, 1 kg) eluting with hexane concentrated to give

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

実験手順: To a solution of lithium wire (2.08 g, 300 mmol) in dry tetrahydrofuran (150 ml) was added methyldiphenylsilyl chloride (15.8 ml, 75 mmol) and a catalytic amount of iodine. The reaction mixture was sonicated for 40 min and then stirred overnight at room temperature. The reaction mixture was cooled to −78° C. and 1,1-difluoroethylene (approx. 225 mmol) was passed through the mixture for 30 min. The mixture was stirred at −78° C. for 2 h and then warmed to room temperature. The reaction mixture was sonicated for 40 min The reaction mixture was cooled to −78° C. The mixture was stirred at −78° C. for 2 h warmed to room temperature

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

実験手順: To a solution of lithium wire (2.08 g, 300 mmol) in dry tetrahydrofuran (150 ml) was added methyldiphenylsilyl chloride (15.8 ml, 75 mmol) and a catalytic amount of iodine. The reaction mixture was sonicated for 40 min and then stirred overnight at room temperature. The reaction mixture was cooled to −78° C. and 1,1-difluoroethylene (approx. 225 mmol) was passed through the mixture for 30 min. The mixture was stirred at −78° C. for 2 h and then warmed to room temperature. The reaction mixture was sonicated for 40 min The reaction mixture was cooled to −78° C. The mixture was stirred at −78° C. for 2 h warmed to room temperature

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

実験手順: To a solution of lithium wire (2.08 g, 300 mmol) in dry tetrahydrofuran (150 ml) was added methyldiphenylsilyl chloride (15.8 ml, 75 mmol) and a catalytic amount of iodine. The reaction mixture was sonicated for 40 min and then stirred overnight at room temperature. The reaction mixture was cooled to −78° C. and 1,1-difluoroethylene (approx. 225 mmol) was passed through the mixture for 30 min. The mixture was stirred at −78° C. for 2 h and then warmed to room temperature. The reaction mixture was sonicated for 40 min The reaction mixture was cooled to −78° C. The mixture was stirred at −78° C. for 2 h warmed to room temperature

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

実験手順: A slurry 89.3 g of Li metal cut into small pieces in 1500 ml dry tetrahydrofuran (THF) under an Ar atmosphere was treated dropwise with neat Ph2MeSiCl (1302.2g, 5.59 moles). During the addition, agitation was provided via a mechanical stirrer and an ice bath was employed as necessary to hold the reaction temperature under 40° C. The mixture was then allowed to stir overnight (16 hr.) at room temperature. The dark red solution of Ph2MeSiLi was then treated with 607.7g (5.59 moles) of Me3SiCl dissolved in 700 ml dry THF. Again an ice bath was utilized to maintain the reaction mixture temperature under 40° C. Near the end of the Me3SiCl addition, the red color of Ph2MeSiLi was completely discharged. Upon completion of the addition, the now essentially colorless mixture was filtered to remove precipitated LiCl and unreacted Li metal. Solvent was removed from the resulting clear solution at reduced pressure and the residual oil fractionally distilled at 0.3 mm Hg to afford 1074.1 g of title compound (71%), bp 108°-110° C. During the addition agitation was provided via a mechanical stirrer and an ice bath under 40° C to maintain the reaction mixture temperature under 40° C Upon completion of the addition the now essentially colorless mixture was filtered to remove precipitated LiCl and unreacted Li metal Solvent was removed from the resulting clear solution at reduced pressure the residual oil fractionally distilled at 0.3 mm Hg

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

実験手順: A slurry 89.3 g of Li metal cut into small pieces in 1500 ml dry tetrahydrofuran (THF) under an Ar atmosphere was treated dropwise with neat Ph2MeSiCl (1302.2g, 5.59 moles). During the addition, agitation was provided via a mechanical stirrer and an ice bath was employed as necessary to hold the reaction temperature under 40° C. The mixture was then allowed to stir overnight (16 hr.) at room temperature. The dark red solution of Ph2MeSiLi was then treated with 607.7g (5.59 moles) of Me3SiCl dissolved in 700 ml dry THF. Again an ice bath was utilized to maintain the reaction mixture temperature under 40° C. Near the end of the Me3SiCl addition, the red color of Ph2MeSiLi was completely discharged. Upon completion of the addition, the now essentially colorless mixture was filtered to remove precipitated LiCl and unreacted Li metal. Solvent was removed from the resulting clear solution at reduced pressure and the residual oil fractionally distilled at 0.3 mm Hg to afford 1074.1 g of title compound (71%), bp 108°-110° C. During the addition agitation was provided via a mechanical stirrer and an ice bath under 40° C to maintain the reaction mixture temperature under 40° C Upon completion of the addition the now essentially colorless mixture was filtered to remove precipitated LiCl and unreacted Li metal Solvent was removed from the resulting clear solution at reduced pressure the residual oil fractionally distilled at 0.3 mm Hg

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

実験手順: A slurry 89.3 g of Li metal cut into small pieces in 1500 ml dry tetrahydrofuran (THF) under an Ar atmosphere was treated dropwise with neat Ph2MeSiCl (1302.2g, 5.59 moles). During the addition, agitation was provided via a mechanical stirrer and an ice bath was employed as necessary to hold the reaction temperature under 40° C. The mixture was then allowed to stir overnight (16 hr.) at room temperature. The dark red solution of Ph2MeSiLi was then treated with 607.7g (5.59 moles) of Me3SiCl dissolved in 700 ml dry THF. Again an ice bath was utilized to maintain the reaction mixture temperature under 40° C. Near the end of the Me3SiCl addition, the red color of Ph2MeSiLi was completely discharged. Upon completion of the addition, the now essentially colorless mixture was filtered to remove precipitated LiCl and unreacted Li metal. Solvent was removed from the resulting clear solution at reduced pressure and the residual oil fractionally distilled at 0.3 mm Hg to afford 1074.1 g of title compound (71%), bp 108°-110° C. During the addition agitation was provided via a mechanical stirrer and an ice bath under 40° C to maintain the reaction mixture temperature under 40° C Upon completion of the addition the now essentially colorless mixture was filtered to remove precipitated LiCl and unreacted Li metal Solvent was removed from the resulting clear solution at reduced pressure the residual oil fractionally distilled at 0.3 mm Hg

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

実験手順: To a solution of lithium wire (2.08 g, 300 mmol) in dry tetrahydrofuran (150 ml) was added methyldiphenylsilyl chloride (15.8 ml, 75 mmol) and a catalytic amount of iodine. The reaction mixture was sonicated for 40 min and then stirred overnight at room temperature. The reaction mixture was cooled to −78° C. and 1,1-difluoroethylene (approx. 225 mmol) was passed through the mixture for 30 min. The mixture was stirred at −78° C. for 2 h and then warmed to room temperature. The reaction mixture was sonicated for 40 min The reaction mixture was cooled to −78° C. The mixture was stirred at −78° C. for 2 h warmed to room temperature

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

実験手順: To a solution of lithium wire (2.08 g, 300 mmol) in dry tetrahydrofuran (150 ml) was added methyldiphenylsilyl chloride (15.8 ml, 75 mmol) and a catalytic amount of iodine. The reaction mixture was sonicated for 40 min and then stirred overnight at room temperature. The reaction mixture was cooled to −78° C. and 1,1-difluoroethylene (approx. 225 mmol) was passed through the mixture for 30 min. The mixture was stirred at −78° C. for 2 h and then warmed to room temperature. The reaction mixture was sonicated for 40 min The reaction mixture was cooled to −78° C. The mixture was stirred at −78° C. for 2 h warmed to room temperature

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

実験手順: The ether and phenylCl are fed in a ratio of 4:1 and the magnesium is fed at a rate to sustain the reaction as monitored by the reactor temperature profile, jacket water temperature rise, and agitator motor amps. The MeSiCl3 feed is varied to obtain a coupling ratio between 0.25 and 0.90 moles of PhCl/mole of MeSiCl3 depending on the ratio of Ph2SiMeCl/PhMeSiCl2 desired. Toluene is fed in at a 3:1 ratio to the PhenylCl in ether. the reaction