trichloro(chloromethyl)silane

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a solution of 6.3 ml (0.050 mol) of chloromethyltrichlorosilane in 75 ml of tetrahydrofuran cooled to -15° C. was added 25 ml of a 2.0 molar solution of p-fluorophenylmagnesium bromide (0.050 mol) at a rate that held the temperature below 0° C. The resulting suspension was stirred 30 minutes at 0° C. then allowed to warm to room temperature over 1 hour. A solution of vinylmagnesium bromide (71 ml, 1.4 molar in tetrahydrofuran) was then added, keeping the temperature below 35° C. The mixture was stirred 2 hours, then washed with saturated ammonium chloride. The aqueous layer was washed with ether-hexanes, and the combined organic layers were washed with brine, dried over sodium sulfate and evaporated. Kugelrohr distillation gave 7.25 g of the title compound as a colorless oil: nmr (CDCl3) 3.1 (2H, s), 5.8-6.7 (6H, m), 7.1, 7.7 (4H, two approximate t); ir (neat) 3060, 2955, 1590, 1497, 1402, 1232, 1162, 1105, 1006, 960, 821, 768 cm-1. the temperature below 0° C to warm to room temperature over 1 hour the temperature below 35° C The mixture was stirred 2 hours washed with saturated ammonium chloride The aqueous layer was washed with ether-hexanes the combined organic layers were washed with brine dried over sodium sulfate evaporated Kugelrohr distillation

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: In the same apparatus and procedure as Example 1 above, 0.20 g (0.75 mmol) of triphenylphosphine, 0.92 g (7.5 mmol) of (chloromethyl)trichlorosilane, and 5.08 g (37.5 mmol) of trichlorosilane were reacted at 150° C. for 42 hrs. The resulting mixture was distilled to give 1.1 g of 1,1,1,3,3,3-hexachloro-1,3-disilapropane (bp; 173-174° C., yield; 50%) and 0.3 g of 1,1,1,3,3-pentachloro-1,3-disilapropane (bp; 166-167° C., yield; 16%). The resulting mixture was distilled

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

実験手順: In the same apparatus and procedure as Example 1 above, 0.20 g (0.75 mmol) of triphenylphosphine, 0.92 g (7.5 mmol) of (chloromethyl)trichlorosilane, and 5.08 g (37.5 mmol) of trichlorosilane were reacted at 150° C. for 42 hrs. The resulting mixture was distilled to give 1.1 g of 1,1,1,3,3,3-hexachloro-1,3-disilapropane (bp; 173-174° C., yield; 50%) and 0.3 g of 1,1,1,3,3-pentachloro-1,3-disilapropane (bp; 166-167° C., yield; 16%). The resulting mixture was distilled

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

実験手順: To a solution of 6.3 ml (0.050 mol) of chloromethyltrichlorosilane in 75 ml of tetrahydrofuran cooled to -15° C. was added 25 ml of a 2.0 molar solution of p-fluorophenylmagnesium bromide (0.050 mol) at a rate that held the temperature below 0° C. The resulting suspension was stirred 30 minutes at 0° C. then allowed to warm to room temperature over 1 hour. A solution of vinylmagnesium bromide (71 ml, 1.4 molar in tetrahydrofuran) was then added, keeping the temperature below 35° C. The mixture was stirred 2 hours, then washed with saturated ammonium chloride. The aqueous layer was washed with ether-hexanes, and the combined organic layers were washed with brine, dried over sodium sulfate and evaporated. Kugelrohr distillation gave 7.25 g of the title compound as a colorless oil: nmr (CDCl3) 3.1 (2H, s), 5.8-6.7 (6H, m), 7.1, 7.7 (4H, two approximate t); ir (neat) 3060, 2955, 1590, 1497, 1402, 1232, 1162, 1105, 1006, 960, 821, 768 cm-1. the temperature below 0° C to warm to room temperature over 1 hour the temperature below 35° C The mixture was stirred 2 hours washed with saturated ammonium chloride The aqueous layer was washed with ether-hexanes the combined organic layers were washed with brine dried over sodium sulfate evaporated Kugelrohr distillation

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

実験手順: To a solution of 6.3 ml (0.050 mol) of chloromethyltrichlorosilane in 75 ml of tetrahydrofuran cooled to -15° C. was added 25 ml of a 2.0 molar solution of p-fluorophenylmagnesium bromide (0.050 mol) at a rate that held the temperature below 0° C. The resulting suspension was stirred 30 minutes at 0° C. then allowed to warm to room temperature over 1 hour. A solution of vinylmagnesium bromide (71 ml, 1.4 molar in tetrahydrofuran) was then added, keeping the temperature below 35° C. The mixture was stirred 2 hours, then washed with saturated ammonium chloride. The aqueous layer was washed with ether-hexanes, and the combined organic layers were washed with brine, dried over sodium sulfate and evaporated. Kugelrohr distillation gave 7.25 g of the title compound as a colorless oil: nmr (CDCl3) 3.1 (2H, s), 5.8-6.7 (6H, m), 7.1, 7.7 (4H, two approximate t); ir (neat) 3060, 2955, 1590, 1497, 1402, 1232, 1162, 1105, 1006, 960, 821, 768 cm-1. the temperature below 0° C to warm to room temperature over 1 hour the temperature below 35° C The mixture was stirred 2 hours washed with saturated ammonium chloride The aqueous layer was washed with ether-hexanes the combined organic layers were washed with brine dried over sodium sulfate evaporated Kugelrohr distillation

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

実験手順: A solution of 25.1 ml (36.8 g, 0.200 mol) of chloromethyltrichlorosilane in 400 ml dry tetrahydrofuran was cooled to -78° under nitrogen and stirred vigorously while 48.0 ml (0.100 mol) of 2.1 molar phenyllithium was slowly dripped in over 1 hour. After stirring another 30 minutes at -78° the solution was allowed to warm to room temperature and evaporated to about 200 ml. Addition of 500 ml ether, filtration to remove precipitated lithium chloride, and evaporation of the filtrate left 25.0 g of liquid. Distillation gave 6.5 g (29%) of the title compound as a colorless liquid: bp 62°-82° (0.15 mm); nmr (CDCl3): δ 3.3 (s, 2) and 7.1-7.9 (m, 5). was slowly dripped in over 1 hour evaporated to about 200 ml Addition of 500 ml ether, filtration to remove precipitated lithium chloride, and evaporation of the filtrate left 25.0 g of liquid Distillation

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

実験手順: A solution of 25.1 ml (36.8 g, 0.200 mol) of chloromethyltrichlorosilane in 400 ml dry tetrahydrofuran was cooled to -78° under nitrogen and stirred vigorously while 48.0 ml (0.100 mol) of 2.1 molar phenyllithium was slowly dripped in over 1 hour. After stirring another 30 minutes at -78° the solution was allowed to warm to room temperature and evaporated to about 200 ml. Addition of 500 ml ether, filtration to remove precipitated lithium chloride, and evaporation of the filtrate left 25.0 g of liquid. Distillation gave 6.5 g (29%) of the title compound as a colorless liquid: bp 62°-82° (0.15 mm); nmr (CDCl3): δ 3.3 (s, 2) and 7.1-7.9 (m, 5). was slowly dripped in over 1 hour evaporated to about 200 ml Addition of 500 ml ether, filtration to remove precipitated lithium chloride, and evaporation of the filtrate left 25.0 g of liquid Distillation

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

実験手順: A mixture of 23.2 g (0.955 mol) of magnesium and 50 mg of iodine in 200 ml of ether was stirred while a solution of 167 g (0.954 mol) of 4-bromofluorobenzene in 600 ml of ether was added at a rate that maintained gentle reflux. After another 2 hours at reflux, the solution was cooled in ice and stirred while a solution of 40 ml (0.32 mol) of chloromethyltrichlorosilane in ether was added dropwise over 40 minutes. The resulting mixture was stirred at room temperature for 17 hours, chilled in ice, treated with 24 ml of isopropanol, stirred another 10 minutes, and filtered. The filtrate was concentrated to a gummy solid, hexanes was added, the resulting slurry was filtered, and the hexanes filtrate was evaporated to leave an oil. Analysis by nmr showed the presence of unreacted chlorosilane, so the oil was dissolved in hexanes containing 30 ml of isopropanol, and the solution was chilled in ice and treated with a solution of 42 ml (0.30 mol) of triethylamine in hexanes. The resulting slurry was stirred at room temperature for 3 hours and filtered, and the filtrate was evaporated to leave an oil. Distillation provided 44.8 g (43%) of the title compound as a colorless liquid: bp 120°-140° (0.1 mm); nD22 1.5211; nmr (CDCl3) 1.2 (6H, d), 3.2 (2H, s), 4.1 (1H, septet), 7.1 (4H, t), 7.7 (4H, d of d). was added at a rate that maintained gentle reflux After another 2 hours at reflux the solution was cooled in ice was added dropwise over 40 minutes chilled in ice stirred another 10 minutes filtered The filtrate was concentrated to a gummy solid, hexanes was added the resulting slurry was filtered the hexanes filtrate was evaporated to leave an oil the solution was chilled in ice The resulting slurry was stirred at room temperature for 3 hours filtered the filtrate was evaporated to leave an oil Distillation

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

実験手順: A mixture of 23.2 g (0.955 mol) of magnesium and 50 mg of iodine in 200 ml of ether was stirred while a solution of 167 g (0.954 mol) of 4-bromofluorobenzene in 600 ml of ether was added at a rate that maintained gentle reflux. After another 2 hours at reflux, the solution was cooled in ice and stirred while a solution of 40 ml (0.32 mol) of chloromethyltrichlorosilane in ether was added dropwise over 40 minutes. The resulting mixture was stirred at room temperature for 17 hours, chilled in ice, treated with 24 ml of isopropanol, stirred another 10 minutes, and filtered. The filtrate was concentrated to a gummy solid, hexanes was added, the resulting slurry was filtered, and the hexanes filtrate was evaporated to leave an oil. Analysis by nmr showed the presence of unreacted chlorosilane, so the oil was dissolved in hexanes containing 30 ml of isopropanol, and the solution was chilled in ice and treated with a solution of 42 ml (0.30 mol) of triethylamine in hexanes. The resulting slurry was stirred at room temperature for 3 hours and filtered, and the filtrate was evaporated to leave an oil. Distillation provided 44.8 g (43%) of the title compound as a colorless liquid: bp 120°-140° (0.1 mm); nD22 1.5211; nmr (CDCl3) 1.2 (6H, d), 3.2 (2H, s), 4.1 (1H, septet), 7.1 (4H, t), 7.7 (4H, d of d). was added at a rate that maintained gentle reflux After another 2 hours at reflux the solution was cooled in ice was added dropwise over 40 minutes chilled in ice stirred another 10 minutes filtered The filtrate was concentrated to a gummy solid, hexanes was added the resulting slurry was filtered the hexanes filtrate was evaporated to leave an oil the solution was chilled in ice The resulting slurry was stirred at room temperature for 3 hours filtered the filtrate was evaporated to leave an oil Distillation

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

実験手順: A suspension of 7.0 g (0.288 mol) of magnesium turnings in 50 ml of ether was stirred under nitrogen while a solution of 50.2 g (0.287 mol) of 4-bromofluorobenzene in 200 ml of ether was added dropwise at a rate that maintained gentle reflux. After another 2 hours at reflux, the mixture was chilled in ice and a solution of 12.0 ml (0.096 mol) of chloromethyltrichlorosilane in 30 ml of ether was added dropwise. The resulting mixture was refluxed for 4 hours, chilled in ice, treated with a solution of 7.5 ml of isopropanol in 20 ml of ether, stirred 5 minutes, and filtered. The filtrate was evaporated to leave a viscous oil that was stirred with hexanes to give a slurry. Filtration under nitrogen and evaporation of the filtrate left a mobile oil that was distilled to give 17.6 g (61%) of the title compound: bp 100°-140° (0.1 mm); nmr (CDCl3) 3.3 (2H, s), 7.1 (4H, t), 7.7 (4H, d of d). was added dropwise at a rate that maintained gentle reflux After another 2 hours at reflux the mixture was chilled in ice The resulting mixture was refluxed for 4 hours chilled in ice filtered The filtrate was evaporated to leave a viscous oil that to give a slurry Filtration under nitrogen evaporation of the filtrate left a mobile oil that was distilled