chloro-[chloro(dimethyl)silyl]-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 4.802 g (25.7 mmol) 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 mL dimethylether was slowly added a solution of 2.285 g (12.8 mmol) sodium 1,2,3,4-tetramethylcyclopentadienide in 30 mL dimethylether. The reaction mixture was stirred several hours, then the solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light-yellow oil. Mass spec: m/e 272 (8%). 1H NMR (C6D6) δ 2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H); 13C NMR (C6D6) δ 135.8, 134.0, 54.4, 14.6, 11.4, 3.2, −2.4. the solvent was removed the residue was extracted with pentane filtered The pentane was removed under reduced pressure

反応条件: temp:135.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reaction mixture containing 10 gm (6×10-2 mole) of p-cyanobenzoyl chloride and 15 gm (1.25 mole equivalent) of 1,2-dichlorotetramethyldisilane was heated to 135° C. during which time the solution became homogeneous. A cocatalyst mixture containing 200 mg. bis(benzonitrile)palladiumdichloride (1 mole %) and 274 mg triphenylphosphine (2 mole %) was then introduced. Carbon monoxide gas evolution began immediately and the reaction was heated at 140° C. for 12 hours while dimethyldichlorosilane was continuously removed. Vacuum distillation gave 7 gm (60% isolated yield) of 4-chlorodimethylsilylbenzonitrile, bp. 93°/0.1 torr, m.p. 40°-43° C. The resulting chlorodimethylsilylbenzonitrile, in the form of a low melting high moisture sensitive solid was hydrolyzed to the corresponding 1,3-bis(4'-benzonitrile)tetramethyldisiloxane in the form of a colorless liquid. The identity of the disiloxane was further confirmed by its NMR and IR spectra. A cocatalyst mixture containing 200 mg was continuously removed Vacuum distillation

反応条件: temp:135.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reaction mixture containing 10 gm (6×10-2 mole) of p-cyanobenzoyl chloride and 15 gm (1.25 mole equivalent) of 1,2-dichlorotetramethyldisilane was heated to 135° C. during which time the solution became homogeneous. A cocatalyst mixture containing 200 mg. bis(benzonitrile)palladiumdichloride (1 mole %) and 274 mg triphenylphosphine (2 mole %) was then introduced. Carbon monoxide gas evolution began immediately and the reaction was heated at 140° C. for 12 hours while dimethyldichlorosilane was continuously removed. Vacuum distillation gave 7 gm (60% isolated yield) of 4-chlorodimethylsilylbenzonitrile, bp. 93°/0.1 torr, m.p. 40°-43° C. The resulting chlorodimethylsilylbenzonitrile, in the form of a low melting high moisture sensitive solid was hydrolyzed to the corresponding 1,3-bis(4'-benzonitrile)tetramethyldisiloxane in the form of a colorless liquid. The identity of the disiloxane was further confirmed by its NMR and IR spectra. A cocatalyst mixture containing 200 mg was continuously removed Vacuum distillation

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

実験手順: To a solution of 4.802 g (25.7 mmol) 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 mL dimethylether was slowly added a solution of 2.285 g (12.8 mmol) sodium 1,2,3,4-tetramethylcyclopentadienide in 30 mL dimethylether. The reaction mixture was stirred several hours, then the solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light-yellow oil. Mass spec: m/e 272 (8%). 1H NMR (C6D6) δ 2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H); 13C NMR (C6D6) δ 135.8, 134.0, 54.4, 14.6, 11.4, 3.2, -2.4. the solvent was removed the residue was extracted with pentane filtered The pentane was removed under reduced pressure

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

実験手順: To a solution of 4.802 g (25.7 mmol) 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 mL dimethylether was slowly added a solution of 2.285 g (12.8 mmol) sodium 1,2,3,4-tetramethylcyclopentadienide in 30 mL dimethylether. The reaction mixture was stirred several hours, then the solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light-yellow oil. Mass spec: m/e 272 (8%). 1H NMR (C6D6) δ 2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H); 13C NMR (C6D6) δ 135.8, 134.0, 54.4, 14.6, 11.4, 3.2, -2.4. the solvent was removed the residue was extracted with pentane filtered The pentane was removed under reduced pressure

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

実験手順: Under a nitrogen gas atmosphere, 4.99 g (9.10 mmol) of 2,7-dibromo-9,9-dioctylfluorene, 20 ml of diethyl ether and 10 ml of toluene were added to a 100 ml three-necked flask equipped with a reflux condenser and a dropping funnel. Under cooling by an ice bath, 6.2 ml (9.92 mmol) of a hexane solution of n-butyllithium (1.6 M) was added dropwise. As the butyllithium was added dropwise, the solution turned red. This solution was agitated “as is” for approximately 1 hour; then, 810 mg (4.33 mmol) of 1,2-dichlorotetramethyldisilane was added, and the resulting mixture was agitated and reacted all night. equipped with a reflux condenser and a dropping funnel Under cooling by an ice bath for approximately 1 hour the resulting mixture was agitated reacted all night

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

実験手順: Under a nitrogen gas atmosphere, 4.99 g (9.10 mmol) of 2,7-dibromo-9,9-dioctylfluorene, 20 ml of diethyl ether and 10 ml of toluene were added to a 100 ml three-necked flask equipped with a reflux condenser and a dropping funnel. Under cooling by an ice bath, 6.2 ml (9.92 mmol) of a hexane solution of n-butyllithium (1.6 M) was added dropwise. As the butyllithium was added dropwise, the solution turned red. This solution was agitated “as is” for approximately 1 hour; then, 810 mg (4.33 mmol) of 1,2-dichlorotetramethyldisilane was added, and the resulting mixture was agitated and reacted all night. equipped with a reflux condenser and a dropping funnel Under cooling by an ice bath for approximately 1 hour the resulting mixture was agitated reacted all night

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

実験手順: To 7.97 g (0.332 mol) of magnesium turnings in 80 mL of THF a mixture of 33.4 g (0.160 mol) of 2-methyl-7-bromo-1H-indene, 30.0 g (0.160 mol) of 1,2-dibromoethane and 420 mL of THF was added dropwise with vigorous stirring at such rate that the mixture is refluxed. Further on, this mixture was additionally refluxed for 30 minutes. The obtained solution was added dropwise with vigorous stirring to a solution of 100 g (0.534 mol) of 1,2-dichloro-1,1,2,2-tetramethyldisilane in 100 mL of THF for 2 hours at room temperature (water bath cooling is required). The resulting mixture was stirred for 12 hours at ambient temperature and then evaporated to dryness. To the residue 100 mL of dry ether was added, and the obtained suspension was stirred for 20 minutes and then filtered through glass frit (G3). The precipitate was washed with 2×100 mL of ether. The combined filtrate was evaporated to dryness, the residue was dried and then rectificated in vacuum, b.p. 140° C.-145° C./1 mm Hg. Yield 26.3 g (58%) of the title product. 1H NMR (CD2Cl2): δ 7.22-7.32 (m, 3H, 4,5,6-H), 6.54 (m, 1H, 3-H), 3.39 (s, 2H, 1,1′-H), 2.21 (s, 3H, 2-Me), 0.66 (m, 3H, SiMe), 0.61 (m, 3H, SiMe), 0.59 (m, 3H, SiMe), 0.50 (m, 3H, SiMe). Anal. Calc. for C14H21ClSi2: C, 59.85; H, 7.53%. Found: C, 59.65; H, 7.72%. was added dropwise is refluxed Further on, this mixture was additionally refluxed for 30 minutes The obtained solution was added dropwise The resulting mixture was stirred for 12 hours at ambient temperature evaporated to dryness To the residue 100 mL of dry ether was added the obtained suspension was stirred for 20 minutes filtered through glass frit (G3) The precipitate was washed with 2×100 mL of ether The combined filtrate was evaporated to dryness the residue was dried

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

実験手順: To a solution of 4.802 g (25.7 mmol) 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 mL dimethylether was slowly added a solution of 2.285 g (12.8 mmol) sodium 1,2,3,4-tetramethylcyclopentadienide in 30 mL dimethylether. The reaction mixture was stirred several hours, then the solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light-yellow oil. Mass spec: m/e 272 (8%). 1H NMR (C6D6) δ 2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H); 13C NMR (C6D6) δ 135.8, 134.0, 54.4, 14.6, 11.4, 3.2, −2.4. the solvent was removed the residue was extracted with pentane filtered The pentane was removed under reduced pressure

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

実験手順: To a solution of 4.802 g (25.7 mmol) 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 mL dimethylether was slowly added a solution of 2.285 g (12.8 mmol) sodium 1,2,3,4-tetramethylcyclopentadienide in 30 mL dimethylether. The reaction mixture was stirred several hours, then the solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light-yellow oil. Mass spec: m/e 272 (8%). 1H NMR (C6D6) δ 2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H); 13C NMR (C6D6) δ 135.8, 134.0, 54.4, 14.6, 11.4, 3.2, −2.4. the solvent was removed the residue was extracted with pentane filtered The pentane was removed under reduced pressure

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

実験手順: To a solution of 4.802 g (25.7 mmol) 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 mL dimethylether was slowly added a solution of 2.285 g (12.8 mmol) sodium 1,2,3,4-tetramethylcyclopentadienide in 30 mL dimethylether. The reaction mixture was stirred several hours, then the solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light-yellow oil. Mass spec: m/e 272 (8%). 1H NMR (C6D6) δ 2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H); 13C NMR (C6D6) δ 135.8, 134.0, 54.4, 14.6, 11.4, 3.2, −2.4. the solvent was removed the residue was extracted with pentane filtered The pentane was removed under reduced pressure

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

実験手順: To a solution of 4.802 g (25.7 mmol) 1,2-dichloro-1,1,2,2-tetramethyldisilane in 50 mL dimethylether was slowly added a solution of 2.285 g (12.8 mmol) sodium 1,2,3,4-tetramethylcyclopentadienide in 30 mL dimethylether. The reaction mixture was stirred several hours, then the solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light-yellow oil. Mass spec: m/e 272 (8%). 1H NMR (C6D6) δ 2.70 (s, 1H), 1.83 (s, 6H), 1.69 (s, 6H), 0.28 (s, 6H), 0.23 (s, 6H); 13C NMR (C6D6) δ 135.8, 134.0, 54.4, 14.6, 11.4, 3.2, −2.4. the solvent was removed the residue was extracted with pentane filtered The pentane was removed under reduced pressure