chloro-dimethyl-phenylsilane

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:; See reaction.notes.procedure_details.

Procedure: To a suspension of 4.4 g of lithium wire cut into small pieces in 200 mL of anhydrous THF stirred under argon and cooled on ice (internal temperature <10° C.) was added dimethylphenyl-chlorosilane in 5 mL portions over 1 hour. The deep red color of the silyl lithium reagent appeared after approximately 0.75 hour. The mixture was stirred on ice for an additional 5 hours (internal temperature remained between 5° C. and 10° C.). The mixture was cooled on a dry ice/acetone bath and 1,1-difluoroethylene was introduced by filling a balloon connected to the reaction mixture and the reagent cylinder using a three-way valve. The balloon was filled with 1,1-difluoroethylene and emptied into the reaction mixture 10 times. The mixture was allowed to warm to room temperature (effervescence observed, probably from unreacted 1,1-difluoroethylene). The mixture was diluted with 200 mL of hexanes and filtered through a cotton wool plug. The filtrate was washed with water, dried, filtered, and concentrated in vacuo. Four fractional distillations under vacuum through a Vigreux column gave 4.6 g of product. cooled on ice (internal temperature <10° C.) The mixture was stirred on ice for an additional 5 hours (internal temperature remained between 5° C. and 10° C.) The mixture was cooled on a dry ice/acetone bath filtered through a cotton wool plug The filtrate was washed with water dried filtered concentrated in vacuo

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

Procedure: The title compound was prepared from the compound of Example e and 1.1 eq dimethylphenylsilyl chloride according to General Method A. Purification by HPLC with 1:9 ethyl acetate/hexanes gave 6.3 g of the desired product as a clear oil, a 91% yield. Purification by HPLC with 1:9 ethyl acetate/hexanes

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

Procedure: The title compound was prepared from the compound of Example e and 1.1 eq dimethylphenylsilyl chloride according to General Method A. Purification by HPLC with 1:9 ethyl acetate/hexanes gave 6.3 g of the desired product as a clear oil, a 91% yield. Purification by HPLC with 1:9 ethyl acetate/hexanes

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

Procedure: Into a 3-necked flask equipped with a stirrer, reflux condenser and a gas conduit, is introduced over a period of 5 minutes with constant agitation and at room temperature, 2-liters [measured at 20° C. and 720 mm Hg (abs.) and thus 0.94 percent based on the total weight of the silanes used], of gaseous hydrogen chloride, into a mixture consisting of 253 grams (1 mol) of diphenyldichlorosilane, 88 grams (1 mol) of tetramethylsilane, 3 grams of trichlorosilane and 3 grams diethylaluminum chloride. Stirring is continued for an additional 4 hours while the mixture is heated under reflux. Fractional distillation yields 30 grams of trimethylchlorosilane, 35 grams of phenyldimethylchlorosilane, 80 grams of diphenylmethylchlorosilane and 74 grams of triphenylchlorosilane. Into a 3-necked flask equipped with a stirrer reflux condenser a gas conduit, is introduced over a period of 5 minutes with constant agitation and at room temperature measured at 20° C. is heated under reflux Fractional distillation

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 38 cm fragment of lithium wire (3.2 mm diameter, 45 mg/cm, 1% sodium content, 0.244 mmole) was cut into 2 mm pieces with a razor blade in a glove bag that had been purged with argon. The fragments were placed in an oven-dried 250 mL round bottom flask and sealed under argon. Then 50 mL of dry THF was added and the mixture was stirred at -10° C. After 10 min. 17.3 mL (100 mmole) of chlorodimethylphenylsilane was added and the mixture was stirred at -10° C. under argon for 36-48 h, until metallation was complete. The cold, dark red solution was transferred by canula to a solution of 6.1 mL (60 mmole) of benzaldehyde in 100 mL of dry THF that had been cooled to -78° C. under argon. The solution was stirred at -78° C. for 45 min and allowed to warm to 0° C. for 30 min. Then it was recooled to -78° C. and quenched by addition of 10 mL of glacial acetic acid in 25 mL of dry THF. The pale yellow solution was partitioned between ether and saturated NH4Cl solution and the ether layer was washed with KHCO3, and brine, dried over MgSO4, and concentrated. The residue was purified by flash chromatography on silica gel (6 cm×30 cm) using 10% ether hexane to afford 11.50 g (79%) of the title compound as a colorless oil. Mass Spectrum (FAB) m/e 243 (M+H). bag that had been purged with argon The fragments were placed in an oven-dried 250 mL round bottom flask sealed under argon Then 50 mL of dry THF was added the mixture was stirred at -10° C. under argon for 36-48 h, until metallation had been cooled to -78° C. under argon The solution was stirred at -78° C. for 45 min to warm to 0° C. for 30 min was recooled to -78° C. quenched by addition of 10 mL of glacial acetic acid in 25 mL of dry THF The pale yellow solution was partitioned between ether and saturated NH4Cl solution the ether layer was washed with KHCO3, and brine dried over MgSO4 concentrated The residue was purified by flash chromatography on silica gel (6 cm×30 cm)

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 38 cm fragment of lithium wire (3.2 mm diameter, 45 mg/cm, 1% sodium content, 0.244 mmole) was cut into 2 mm pieces with a razor blade in a glove bag that had been purged with argon. The fragments were placed in an oven-dried 250 mL round bottom flask and sealed under argon. Then 50 mL of dry THF was added and the mixture was stirred at -10° C. After 10 min. 17.3 mL (100 mmole) of chlorodimethylphenylsilane was added and the mixture was stirred at -10° C. under argon for 36-48 h, until metallation was complete. The cold, dark red solution was transferred by canula to a solution of 6.1 mL (60 mmole) of benzaldehyde in 100 mL of dry THF that had been cooled to -78° C. under argon. The solution was stirred at -78° C. for 45 min and allowed to warm to 0° C. for 30 min. Then it was recooled to -78° C. and quenched by addition of 10 mL of glacial acetic acid in 25 mL of dry THF. The pale yellow solution was partitioned between ether and saturated NH4Cl solution and the ether layer was washed with KHCO3, and brine, dried over MgSO4, and concentrated. The residue was purified by flash chromatography on silica gel (6 cm×30 cm) using 10% ether hexane to afford 11.50 g (79%) of the title compound as a colorless oil. Mass Spectrum (FAB) m/e 243 (M+H). bag that had been purged with argon The fragments were placed in an oven-dried 250 mL round bottom flask sealed under argon Then 50 mL of dry THF was added the mixture was stirred at -10° C. under argon for 36-48 h, until metallation had been cooled to -78° C. under argon The solution was stirred at -78° C. for 45 min to warm to 0° C. for 30 min was recooled to -78° C. quenched by addition of 10 mL of glacial acetic acid in 25 mL of dry THF The pale yellow solution was partitioned between ether and saturated NH4Cl solution the ether layer was washed with KHCO3, and brine dried over MgSO4 concentrated The residue was purified by flash chromatography on silica gel (6 cm×30 cm)

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

Procedure: The title compound was prepared from the compound of Example e and 1.1 eq dimethylphenylsilyl chloride according to General Method A. Purification by HPLC with 1:9 ethyl acetate/hexanes gave 6.3 g of the desired product as a clear oil, a 91% yield. Purification by HPLC with 1:9 ethyl acetate/hexanes

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

Procedure: According to the procedure as described in Example 1,2,2-dimethyl-1-methoxy-3-[(dimethylphenylsilyl)oxy]propane was prepared from intermediate 2,2-dimethyl-3-methoxy-1-propanol and reagent dimethylphenylsilyl chloride.

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

Procedure: According to the procedure as described in Example 1,2,2-dimethyl-1-methoxy-3-[(dimethylphenylsilyl)oxy]propane was prepared from intermediate 2,2-dimethyl-3-methoxy-1-propanol and reagent dimethylphenylsilyl chloride.