hydroxy(trimethyl)silane

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

実験手順: This reaction proceeds slowly without diethylether but reacts faster at reflux temperatures. Trimethylsilanol is condensed during the HMDS distillation step to give HMDSO, which reacts as shown above. reacts faster at reflux temperatures condensed during the HMDS distillation step

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

実験手順: Ethyl 3-(1-methyl-1H-pyrazol-4-yl)-3-(6-(trifluoromethyl)pyridin-3-yl)propanoate (1.15 g, 3.51 mmol) was mixed with trimethylsilanol, sodium salt solution in THF (30 ml, 30.0 mmol, 1 molar) and stirred for 24 hours at room temperature. Trimethylsilanol, sodium salt solution in THF (30 ml, 30.0 mmol, 1 molar) added and mixture stiffed overnight at room temperature, LCMS shows incomplete comversion and reaction heated at reflux for 3 hours. The mixture was cooled on an ice bath and HCl in Et2O (48.0 g, 40 ml, 80 mmol, 2 molar) was added and after 10 min the mixture was concentrated in vacuo. The crude reaction mixture was then suspended dry THF (150 mL) and the solid filtred off. The liquid phase was concentrated in vacuo and used for next step without purification. 3-(1-methyl-1H-pyrazol-4-yl)-3-(6-(trifluoromethyl)pyridin-3-yl)propanoic acid (0.531 g, 1.774 mmol) dissolved in tert-butanol (10 ml. TEA (0.395 g, 0.544 ml, 3.90 mmol) and diphenylphosphoryl azide (0.59 g, 0.46 ml, 2.1 mmol) were added. Heated at 80° C. for 29 hours. The reaction was poured into H2O (50 mL) and extracted with EA (3×50 mL), the combined org. phases washed with brine, dried over MgSO4, concentrated in vacuo and purified by flash chromatography to yield 49 mg (7%) tert-butyl (2-(1-methyl-1H-pyrazol-4-yl)-2-(6-(trifluoromethyl)pyridin-3-yl)ethyl)carbamate. mixture stiffed overnight at room temperature comversion and reaction heated at reflux for 3 hours The mixture was cooled on an ice bath was concentrated in vacuo The crude reaction mixture The liquid phase was concentrated in vacuo used for next step without purification Heated at 80° C. for 29 hours extracted with EA (3×50 mL) phases washed with brine dried over MgSO4 concentrated in vacuo purified by flash chromatography

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

実験手順: Ethyl 3-(1-methyl-1H-pyrazol-4-yl)-3-(6-(trifluoromethyl)pyridin-3-yl)propanoate (1.15 g, 3.51 mmol) was mixed with trimethylsilanol, sodium salt solution in THF (30 ml, 30.0 mmol, 1 molar) and stirred for 24 hours at room temperature. Trimethylsilanol, sodium salt solution in THF (30 ml, 30.0 mmol, 1 molar) added and mixture stiffed overnight at room temperature, LCMS shows incomplete comversion and reaction heated at reflux for 3 hours. The mixture was cooled on an ice bath and HCl in Et2O (48.0 g, 40 ml, 80 mmol, 2 molar) was added and after 10 min the mixture was concentrated in vacuo. The crude reaction mixture was then suspended dry THF (150 mL) and the solid filtred off. The liquid phase was concentrated in vacuo and used for next step without purification. 3-(1-methyl-1H-pyrazol-4-yl)-3-(6-(trifluoromethyl)pyridin-3-yl)propanoic acid (0.531 g, 1.774 mmol) dissolved in tert-butanol (10 ml. TEA (0.395 g, 0.544 ml, 3.90 mmol) and diphenylphosphoryl azide (0.59 g, 0.46 ml, 2.1 mmol) were added. Heated at 80° C. for 29 hours. The reaction was poured into H2O (50 mL) and extracted with EA (3×50 mL), the combined org. phases washed with brine, dried over MgSO4, concentrated in vacuo and purified by flash chromatography to yield 49 mg (7%) tert-butyl (2-(1-methyl-1H-pyrazol-4-yl)-2-(6-(trifluoromethyl)pyridin-3-yl)ethyl)carbamate. mixture stiffed overnight at room temperature comversion and reaction heated at reflux for 3 hours The mixture was cooled on an ice bath was concentrated in vacuo The crude reaction mixture The liquid phase was concentrated in vacuo used for next step without purification Heated at 80° C. for 29 hours extracted with EA (3×50 mL) phases washed with brine dried over MgSO4 concentrated in vacuo purified by flash chromatography

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

実験手順: This reaction proceeds slowly without diethylether but reacts faster at reflux temperatures. Trimethylsilanol is condensed during the HMDS distillation step to give HMDSO, which reacts as shown above. reacts faster at reflux temperatures condensed during the HMDS distillation step

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

実験手順: The following were ingredients were introduced into a stirrer-equipped four-neck flask: 164.8 g (651.2 mmol) diphenyldichlorosilane and 300 mL tetrahydrofuran. The resultant mixture was stirred at room temperature while a mixture of 60 g (542.7 mmol) of 81.4% pure trimethylsilanol and 65.9 g (651.2 mmol) of triethylamine was added dropwise. Stirring at room temperature was continued for an additional hour following completion of the addition, at which time the salt formed as a by-product of the reaction was removed by filtration. The filtrate was then distilled under reduced pressure to yield 118.7 g of a fraction boiling at 136.5° C.-142° C. under of 2 mm Hg, equivalent to a 71.4% yield of trimethylsiloxydiphenylchlorosilane. Analysis of this product by gas chromatography (GLC), nuclear magnetic resonance (NMR), and infrared spectrochemical analysis (IR) confirmed it to be trimethylsiloxydiphenylchlorosilane with the following structural formula. ##STR6## were introduced into a stirrer-equipped four-neck flask was added dropwise was continued for an additional hour completion of the addition at which time the salt formed as a by-product of the reaction was removed by filtration The filtrate was then distilled under reduced pressure

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

実験手順: Ethyl 3-(1-methyl-1H-pyrazol-4-yl)-3-(6-(trifluoromethyl)pyridin-3-yl)propanoate (1.15 g, 3.51 mmol) was mixed with trimethylsilanol, sodium salt solution in THF (30 ml, 30.0 mmol, 1 molar) and stirred for 24 hours at room temperature. Trimethylsilanol, sodium salt solution in THF (30 ml, 30.0 mmol, 1 molar) added and mixture stiffed overnight at room temperature, LCMS shows incomplete comversion and reaction heated at reflux for 3 hours. The mixture was cooled on an ice bath and HCl in Et2O (48.0 g, 40 ml, 80 mmol, 2 molar) was added and after 10 min the mixture was concentrated in vacuo. The crude reaction mixture was then suspended dry THF (150 mL) and the solid filtred off. The liquid phase was concentrated in vacuo and used for next step without purification. 3-(1-methyl-1H-pyrazol-4-yl)-3-(6-(trifluoromethyl)pyridin-3-yl)propanoic acid (0.531 g, 1.774 mmol) dissolved in tert-butanol (10 ml. TEA (0.395 g, 0.544 ml, 3.90 mmol) and diphenylphosphoryl azide (0.59 g, 0.46 ml, 2.1 mmol) were added. Heated at 80° C. for 29 hours. The reaction was poured into H2O (50 mL) and extracted with EA (3×50 mL), the combined org. phases washed with brine, dried over MgSO4, concentrated in vacuo and purified by flash chromatography to yield 49 mg (7%) tert-butyl (2-(1-methyl-1H-pyrazol-4-yl)-2-(6-(trifluoromethyl)pyridin-3-yl)ethyl)carbamate. mixture stiffed overnight at room temperature comversion and reaction heated at reflux for 3 hours The mixture was cooled on an ice bath was concentrated in vacuo The crude reaction mixture The liquid phase was concentrated in vacuo used for next step without purification Heated at 80° C. for 29 hours extracted with EA (3×50 mL) phases washed with brine dried over MgSO4 concentrated in vacuo purified by flash chromatography

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

実験手順: This reaction proceeds slowly without diethylether but reacts faster at reflux temperatures. Trimethylsilanol is condensed during the HMDS distillation step to give HMDSO, which reacts as shown above. reacts faster at reflux temperatures condensed during the HMDS distillation step