chloro(triphenyl)silane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: tert-BuLi (1.7 M in pentane, 58 ml, 99 mmol) is added slowly to a cold solution (−78° C.) of 3,6-dibromo-9-triphenylsilylcarbazole (90% purity, see i), 13 g, 22 mmol) in dry THF (1000 ml). After stirring at −78° C. for two hours, ClSiPh3 (34 g, 115 mmol) in dry THF is added. The mixture is stirred overnight, and saturated NH4Cl solution is added. The resulting salt is filtered off, and the organic phase is separated from the aqueous phase. The aqueous phase is extracted with CH2Cl2. The organic phase is washed twice with water. The combined organic phases are dried over Na2SO4. After column chromatography (SiO2; 5:1 cyclohexane:CH2Cl2), the pure product is obtained (Rf˜0.3, 11 g, 53%). The mixture is stirred overnight The resulting salt is filtered off the organic phase is separated from the aqueous phase The aqueous phase is extracted with CH2Cl2 The organic phase is washed twice with water The combined organic phases are dried over Na2SO4 After column chromatography (SiO2; 5:1 cyclohexane:CH2Cl2), the pure product is obtained (Rf˜0.3, 11 g, 53%)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: NaH (60% dispersion in oil, 1.5 g, 37 mmol) is added slowly to a cold solution (0° C.) of 3,6-dibromocarbazole (10.4 g, 31 mmol) in dry THF (1000 ml). After stirring for two hours, a solution of ClSiPh3 (18.7 g, 62 mmol) in dry THF (200 ml) is added at 0° C. The mixture is stirred overnight, and saturated NH4Cl solution is added. The resulting salt is filtered off, and the organic phase is separated from the aqueous phase. The aqueous phase is extracted with CH2Cl2. The organic phase is washed twice with water. The combined organic phases are dried over Na2SO4. Filtration through SiO2 gives the desired product (quantitative). The mixture is stirred overnight The resulting salt is filtered off the organic phase is separated from the aqueous phase The aqueous phase is extracted with CH2Cl2 The organic phase is washed twice with water The combined organic phases are dried over Na2SO4 Filtration through SiO2

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3,6-dibromocarbazole (9.1 g, 1 eq) in dry THF (400 ml) at 0° C. under argon is admixed slowly with NaH (60% in mineral oil, 1.3 g, 1.2 eq) and stirred at 0° C. for 2 h. After adding a solution of chlorotriethylsilane (5.1 g, 1.2 eq) in dry THF (80 ml), the solution is stirred at RT (room temperature) for 1 h. The solution is cooled to −78° C. and admixed with n-butyllithium (1.6 M in hexane, 43.8 ml, 2.5 eq) and stirred at −78° C. for 1 h. After adding a solution of chlorotriphenylsilane (29.8 g, 3.5 eq) in dry THF (100 ml) at −78° C., the mixture is warmed to room temperature overnight with stirring. Excess butyllithium is hydrolyzed with saturated ammonium chloride solution. The precipitated product is filtered off and washed thoroughly with methylene chloride. The combined methylene chloride filtrates are extracted by shaking with water and dried over sodium sulfate. The organic phase is admixed with tetra-n-butylammonium fluoride (TBAF, 1 M in THF, 2 ml) and stirred at RT for 4 h. The mixture is concentrated down to 100 ml. The resulting precipitate is filtered and washed with n-hexane. Yield 66%. at 0° C. the solution is stirred at RT (room temperature) for 1 h The solution is cooled to −78° C. stirred at −78° C. for 1 h the mixture is warmed to room temperature overnight with stirring The precipitated product is filtered off washed thoroughly with methylene chloride The combined methylene chloride filtrates are extracted by shaking with water dried over sodium sulfate stirred at RT for 4 h The mixture is concentrated down to 100 ml The resulting precipitate is filtered washed with n-hexane

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 9-(3-methoxyphenyl)-3,6-dibromo-9H-carbazole (26 g, 1 eq) in dry THF (700 ml) is admixed slowly at −78° C. under argon with n-butyllithium (1.6 M in hexane, 41 ml, 1 eq) and stirred at −78° C. for 2 h. After a solution of chlorotriphenylsilane (30 g, 1.5 eq) in dry THF (150 ml) had been added at −78° C., the mixture was warmed to room temperature overnight with stirring. Excess butyllithium is hydrolyzed with saturated ammonium chloride solution. The precipitated reaction product is filtered off and washed thoroughly with methylene chloride. The combined methylene chloride filtrates are extracted with water and concentrated to dryness. The residue is stirred with acetone and filtered off. Yield 74%. the mixture was warmed to room temperature overnight with stirring The precipitated reaction product is filtered off washed thoroughly with methylene chloride The combined methylene chloride filtrates are extracted with water concentrated to dryness The residue is stirred with acetone filtered off

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the method of Wiberg et al [Wiberg et al, Angew. Chem. Internat'l Ed. Engl., 1, 335 (1962)] in an inert atmosphere enclosure a solution of triphenylsilylchloride (73.9 g, 0.251 mol) in tetrahydrofuran (400 ml) was stirred with lithium azide (15.3 g, 0.312 mol) at room temperature over a period of 115 hr. After filtration, the solvent was removed in vacuo. The resulting white solid was boiled with heptane (350 ml), filtered hot and allowed to crystalline. Triphenylsilyl azide, 65.5 g (86.3% yield), mp 82°-84° C was obtained. The melting point and infrared spectrum were identical with that of an authentic sample. After filtration the solvent was removed in vacuo filtered hot

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 9.0 gm (0.03 mole) of 19-hydroxy-4-androstene-3,17-dione, 11.8 gm (0.04 mole) of triphenylchlorosilane and 9.6 gm (0.12 mole) of pyridine contained in 100 ml of benzene is refluxed for a period of 18 hours. The resulting suspension is filtered and concentrated in vacuo to a yellow oil. The oil is placed on a silica gel chromatographic column packed in chloroform which is further eluted with chloroform. The chloroform eluant is evaporated to dryness in vacuo and recrystallized from methanol to yield 19-(triphenylsiloxy)-4-androstene-3,17-dione methanolate having a m.p. of 100°-2° C., uv max (MeOH) 223 nm (ε30,430), 242 nm (ε17,300). is refluxed for a period of 18 hours The resulting suspension is filtered concentrated in vacuo to a yellow oil is further eluted with chloroform The chloroform eluant is evaporated to dryness in vacuo recrystallized from methanol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a nitrogen atmosphere, 12 g (35.7 mmol) of 9,10-dibromoanthracene, and 300 ml of tetrahydrofuran (THF) were added to a round-bottom flask. Next, 14.4 ml (35.7 mmol, 2.5M) of n-butyl lithium was added dropwise slowly into the round-bottom flask at −78° C. After mixing and reacting for 30 min, 12 g (40.7 mmol) triphenylsilyl chloride with 50 ml THF were added dropwise slowly into the round-bottom flask at −78° C. After reacting at room temperature for 24 hours, the resulting mixture was subjected to extraction with a mixed solvent (ethyl acetate:H2O), dried over anhydrous MgSO4, filtered, and condensed, then the crude product was purified by column chromatography (n-hexane/acetyl acetate=15/1), A 9.0 g of pure 9-bromo-10-triphenysilyl anthracene was collected. After mixing After reacting at room temperature for 24 hours the resulting mixture was subjected to extraction with a mixed solvent (ethyl acetate:H2O) dried over anhydrous MgSO4 filtered condensed the crude product was purified by column chromatography (n-hexane/acetyl acetate=15/1) A 9.0 g of pure 9-bromo-10-triphenysilyl anthracene was collected