dichloro(diethyl)silane

反応条件: temp:0.00; pressure:0.00; stir:

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: To a −78° C. solution of 2-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (1.34 g, 5.0 mmol) in 6.9 mL of THF was added n-butyllithium (1.6 M, 3.13 ml, 5.0 mmol). After ten minutes, the solution was added via canula to a B78° C. solution of diethyldichlorosilane (0.61 mL, 5.0 mmol) and THF (4.4 mL) and stirring continued for 1 hour. In a second flask containing 4-bromobenzyl tert-butyldiphenylsilyl ether (Compound 1, 3.19 g, 7.5 μmmol) and THF (2 mL) at −78° C. was added n-butyllithium (1.6 M, 4.69 mL, 7.5 mmol). After ten minutes, the contents of the second flask were added via canula to the first flask. After 30 minutes at −78° C., the reaction was quenched by the addition of 5 mL of saturated aqueous NH4Cl. The solution was poured into a separatory funnel containing water and hexane. The layers were separated and the aqueous layer was extracted 3 times with hexane. The combined organic layers were washed once with brine, and dried over magnesium sulfate, and the solvents were removed under reduced pressure. The residue was dissolved in 20 mL of THF and treated with 3.2 g of tetrabutylammonium flouride (Tbaf) adsorbed onto silica gel (1-1.6 mmol flouride per gram). The suspension was stirred for 5 hours at room temperature and then the silica gel was washed with ether, and the separated ether extracts were dried over magnesium sulfate. The filtered solvents were removed under reduced pressure and the residue purified by silica gel chromatography (9:1, hexane:ethyl acetate) to give the title compound. After ten minutes the solution was added via canula to a B78° C After ten minutes the contents of the second flask were added via canula to the first flask After 30 minutes at −78° C. the reaction was quenched by the addition of 5 mL of saturated aqueous NH4Cl The solution was poured into a separatory funnel containing water and hexane The layers were separated the aqueous layer was extracted 3 times with hexane The combined organic layers were washed once with brine dried over magnesium sulfate the solvents were removed under reduced pressure The residue was dissolved in 20 mL of THF treated with 3.2 g of tetrabutylammonium flouride (Tbaf) the silica gel was washed with ether the separated ether extracts were dried over magnesium sulfate The filtered solvents were removed under reduced pressure the residue purified by silica gel chromatography (9:1, hexane:ethyl acetate)

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

実験手順: A similar procedure to the one reported in EXAMPLE 2 was followed except dichlorodiethylsilane (5.12 g, 32.5 mmol, 1 eq) was used as the substrate along with 2eq each of CF3H and KHMDS to obtain pure diethyl bis(trifluoromethyl)silane 3.2 g, 44% yield. 1H NMR (400 MHz): δ 1.08 (m, CH2), 1.16 (m, CH3); 13C NMR (100.5 MHz): δ-1.10 (s, CH2), 5.55 (s, CH3), 128.6 (qq, 1JC—F=319 Hz, 3.35 Hz, CF3); 19F NMR (376.3 MHz): δ-60.2 (s); 29Si NMR (79.5 MHz): δ-2.43 (sept, 2JSi—F=39.4 Hz, 1 Si).

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

実験手順: One mole of diethyldichlorosilane can be dissolved in one liter of tetrahydrofuran, or similar solvent, under an atmosphere of nitrogen, and one mole of lithium dimethylamide can be slowly added with stirring over a one hour period, then stirred overnight. All of the volatiles can be vacuum transferred off and fractionally distilled to yield the product, dimethylaminodiethylchlorosilane. This product can be dissolved in tetrahydrofuran, or similar solvent, under a nitrogen atmosphere. One mole of water can be dissolved in 100 ml of tetrahydrofuran, or similar solvent, and can be added slowly over a one hour period at zero degrees centigrade. The resulting mixture can be filtered, and the filtrate fractionally distilled to give the product, dimethylaminodiethylsilanol. One equivalent of this product can be dissolved in tetrahydrofuran, or in a similar solvent, and treated with one equivalent of n-butyl lithium solution. The mixture can be cooled to zero degrees centigrade, and one equivalent of copper chloride can be added over 30 minutes. The mixture would be allowed to warm to room temperature, filtered, solvent stripped away, and the resulting mixture can be heated under vacuum to distill out the product, [Cu—NMe2-SiEt2-O—Cu—NMe2-SiEt2-O—Cu—]. stirred overnight fractionally distilled

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

実験手順: One mole of diethyldichlorosilane can be dissolved in one liter of tetrahydrofuran, or similar solvent, under an atmosphere of nitrogen, and one mole of lithium dimethylamide can be slowly added with stirring over a one hour period, then stirred overnight. All of the volatiles can be vacuum transferred off and fractionally distilled to yield the product, dimethylaminodiethylchlorosilane. This product can be dissolved in tetrahydrofuran, or similar solvent, under a nitrogen atmosphere. One mole of water can be dissolved in 100 ml of tetrahydrofuran, or similar solvent, and can be added slowly over a one hour period at zero degrees centigrade. The resulting mixture can be filtered, and the filtrate fractionally distilled to give the product, dimethylaminodiethylsilanol. One equivalent of this product can be dissolved in tetrahydrofuran, or in a similar solvent, and treated with one equivalent of n-butyl lithium solution. The mixture can be cooled to zero degrees centigrade, and one equivalent of copper chloride can be added over 30 minutes. The mixture would be allowed to warm to room temperature, filtered, solvent stripped away, and the resulting mixture can be heated under vacuum to distill out the product, [Cu—NMe2-SiEt2-O—Cu—NMe2-SiEt2-O—Cu—]. stirred overnight fractionally distilled

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

実験手順: Under nitrogen atmosphere, 2-methoxy-1-bromo-3-tert-butyl-5-methylbenzene (20.00 g, 77.77 mmol) was dissolved in 200 mL of diethyl ether. A 1.57 M hexane solution of n-butyllithium (59.44 mL, 93.32 mmol) was dropwise added at −50° C. or lower, and a temperature was raised to room temperature, followed by stirring for 1 hour. All the amount of diethyldichlorosilane (24.44 g, 155.54 mmol) was added to the mixture at once at −50° C. or lower, and a temperature was gradually raised to room temperature. After being refluxed for 1 hour, the solution was concentrated under reduced pressure. Hexane was added, the insolubles were filtered off with a Celite filter, and the filtrate was concentrated under reduced pressure. Concentration was further continued at 70° C. under reduced pressure for 3 hours to obtain (2-methoxy-3-tert-butyl-5-methylphenyl)chlorodimethylsilane. Resultant (2-methoxy-3-tert-butyl-5-methylphenyl)chlorodimethylsilane was used in a subsequent reaction without further purification. lower, and a temperature was gradually raised to room temperature After being refluxed for 1 hour the solution was concentrated under reduced pressure Hexane was added the insolubles were filtered off with a Celite filter the filtrate was concentrated under reduced pressure Concentration was further continued at 70° C. under reduced pressure for 3 hours

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

実験手順: Under nitrogen atmosphere, 2-methoxy-1-bromo-3-tert-butyl-5-methylbenzene (20.00 g, 77.77 mmol) was dissolved in 200 mL of diethyl ether. A 1.57 M hexane solution of n-butyllithium (59.44 mL, 93.32 mmol) was dropwise added at −50° C. or lower, and a temperature was raised to room temperature, followed by stirring for 1 hour. All the amount of diethyldichlorosilane (24.44 g, 155.54 mmol) was added to the mixture at once at −50° C. or lower, and a temperature was gradually raised to room temperature. After being refluxed for 1 hour, the solution was concentrated under reduced pressure. Hexane was added, the insolubles were filtered off with a Celite filter, and the filtrate was concentrated under reduced pressure. Concentration was further continued at 70° C. under reduced pressure for 3 hours to obtain (2-methoxy-3-tert-butyl-5-methylphenyl)chlorodimethylsilane. Resultant (2-methoxy-3-tert-butyl-5-methylphenyl)chlorodimethylsilane was used in a subsequent reaction without further purification. lower, and a temperature was gradually raised to room temperature After being refluxed for 1 hour the solution was concentrated under reduced pressure Hexane was added the insolubles were filtered off with a Celite filter the filtrate was concentrated under reduced pressure Concentration was further continued at 70° C. under reduced pressure for 3 hours

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

実験手順: To a −78° C. solution of 2-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (1.34 g, 5.0 mmol) in 6.9 mL of THF was added n-butyllithium (1.6 M, 3.13 mL, 5.0 mmol). After ten minutes, the solution was added via cannula to a B78° C. solution of diethyldichlorosilane (0.61 mL, 5.0 mmol) and THF (4.4 mL) and stirring continued for 1 hour. In a second flask containing 4-bromobenzyl tert-butyldiphenylsilyl ether (Compound 1, 3.19 g, 7.5 mmol) and THF (2 mL) at −78° C. was added n-butyllithium (1.6 M, 4.69 mL, 7.5 mmol). After ten minutes, the contents of the second flask were added via canula to the first flask. After 30 minutes at −78° C., the reaction was quenched by the addition of 5 mL of saturated aqueous NH4Cl. The solution was poured into a separatory funnel containing water and hexane. The layers were separated and the aqueous layer was extracted 3 times with hexane. The combined organic layers were washed once with brine, and dried over magnesium sulfate, and the solvents were removed under reduced pressure. The residue was dissolved in 20 mL of THF and treated with 3.2 g of tetrabutylammonium flouride (Tbaf) adsorbed onto silica gel (1-1.6 mmol flouride per gram). The suspension was stirred for 5 hours at room temperature and then the silica gel was washed with ether, and the separated ether extracts were dried over magnesium sulfate. The filtered solvents were removed under reduced pressure and the residue purified by silica gel chromatography (9:1, hexane:ethyl acetate) to give the title compound. After ten minutes the solution was added via cannula to a B78° C After ten minutes the contents of the second flask were added via canula to the first flask After 30 minutes at −78° C. the reaction was quenched by the addition of 5 mL of saturated aqueous NH4Cl The solution was poured into a separatory funnel containing water and hexane The layers were separated the aqueous layer was extracted 3 times with hexane The combined organic layers were washed once with brine dried over magnesium sulfate the solvents were removed under reduced pressure The residue was dissolved in 20 mL of THF treated with 3.2 g of tetrabutylammonium flouride (Tbaf) the silica gel was washed with ether the separated ether extracts were dried over magnesium sulfate The filtered solvents were removed under reduced pressure the residue purified by silica gel chromatography (9:1, hexane:ethyl acetate)

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

実験手順: To a −78° C. solution of 2-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (1.34 g, 5.0 mmol) in 6.9 mL of THF was added n-butyllithium (1.6 M, 3.13 ml, 5.0 mmol). After ten minutes, the solution was added via canula to a B78° C. solution of diethyldichlorosilane (0.61 mL, 5.0 mmol) and THF (4.4 mL) and stirring continued for 1 hour. In a second flask containing 4-bromobenzyl tert-butyldiphenylsilyl ether (Compound 1, 3.19 g, 7.5 μmmol) and THF (2 mL) at −78° C. was added n-butyllithium (1.6 M, 4.69 mL, 7.5 mmol). After ten minutes, the contents of the second flask were added via canula to the first flask. After 30 minutes at −78° C., the reaction was quenched by the addition of 5 mL of saturated aqueous NH4Cl. The solution was poured into a separatory funnel containing water and hexane. The layers were separated and the aqueous layer was extracted 3 times with hexane. The combined organic layers were washed once with brine, and dried over magnesium sulfate, and the solvents were removed under reduced pressure. The residue was dissolved in 20 mL of THF and treated with 3.2 g of tetrabutylammonium flouride (Tbaf) adsorbed onto silica gel (1-1.6 mmol flouride per gram). The suspension was stirred for 5 hours at room temperature and then the silica gel was washed with ether, and the separated ether extracts were dried over magnesium sulfate. The filtered solvents were removed under reduced pressure and the residue purified by silica gel chromatography (9:1, hexane:ethyl acetate) to give the title compound. After ten minutes the solution was added via canula to a B78° C After ten minutes the contents of the second flask were added via canula to the first flask After 30 minutes at −78° C. the reaction was quenched by the addition of 5 mL of saturated aqueous NH4Cl The solution was poured into a separatory funnel containing water and hexane The layers were separated the aqueous layer was extracted 3 times with hexane The combined organic layers were washed once with brine dried over magnesium sulfate the solvents were removed under reduced pressure The residue was dissolved in 20 mL of THF treated with 3.2 g of tetrabutylammonium flouride (Tbaf) the silica gel was washed with ether the separated ether extracts were dried over magnesium sulfate The filtered solvents were removed under reduced pressure the residue purified by silica gel chromatography (9:1, hexane:ethyl acetate)

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

実験手順: A similar procedure to the one reported in EXAMPLE 2 was followed except dichlorodiethylsilane (5.12 g, 32.5 mmol, 1 eq) was used as the substrate along with 2eq each of CF3H and KHMDS to obtain pure diethyl bis(trifluoromethyl)silane 3.2 g, 44% yield. 1H NMR (400 MHz): δ 1.08 (m, CH2), 1.16 (m, CH3); 13C NMR (100.5 MHz): δ-1.10 (s, CH2), 5.55 (s, CH3), 128.6 (qq, 1JC—F=319 Hz, 3.35 Hz, CF3); 19F NMR (376.3 MHz): δ-60.2 (s); 29Si NMR (79.5 MHz): δ-2.43 (sept, 2JSi—F=39.4 Hz, 1 Si).