trichloro(methyl)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:; See reaction.notes.procedure_details.

Procedure: Ethyl 4-{4-[4-(dimethoxymethyl)anilino]-1-piperidinyl}benzoate (0.63 g, 01.53 mmol) was added to a pre-prepared mixture of sodium iodide (0.572 g, 3.82 mmol) and trichloro(methyl)silane (0.36 mL, 3.07 mmol) in anhydrous acetonitrile. The reaction was stirred at ambient temperature for 3 minutes. Dichloromethane was added and the reaction washed with 10% sodium thiosulfate solution, water and brine. The organic layer was dried with anhydrous magnesium sulfate, filtered and the solvent partially removed in vacuo. The aldehyde solution was used directly and treated with methanol, tetrahydrofuran, acetic acid (0.091 mL, 1.53 mmol), N-{5-[(1R)-2-amino-1-hydroxyethyl]-2-hydroxyphenyl)methanesulfonamide (0.377 g, 0.1.53 mmol) followed by sodium cyanoborohydride (0.105 g, 1.53 mmol). The reaction was stirred at ambient temperature overnight. The reaction was taken to dryness in vacuo, adsorbed onto silica and purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide). The hydrochoride salt of the title compound was generated from anhydrous etheral hydrochloric acid in ethyl acetate (0.14 g, 0.221 mmol). the reaction washed with 10% sodium thiosulfate solution, water and brine The organic layer was dried with anhydrous magnesium sulfate filtered the solvent partially removed in vacuo The reaction was stirred at ambient temperature overnight purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide)

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

Procedure: N-[4-(2,2-Dimethoxyethyl)phenyl]-1-[4-(1-piperidinylsulfonyl)phenyl]-4-piperidinamine (0.395 g, 0.81 mmol) was added to a pre-prepared mixture of sodium iodide (0.303 g, 2.02 mmol) and trichloro(methyl)silane (0.191 mL, 1.62 mmol) in anhydrous acetonitrile. The reaction was stirred at ambient temperature for 3 minutes. Dichloromethane was added and the reaction washed with 10% sodium thiosulfate solution, water and brine. The organic layer was dried with anhydrous magnesium sulfate, filtered and the solvent partially removed in vacuo. The aldehyde solution was used directly and treated with methanol, acetic acid (0.06 mL, 1.01 mmol), N-{5-[(1R)-2-amino-1-hydroxyethyl]-2-hydroxyphenyl}methanesulfonamide (0.20 g, 0.812 mmol) followed by sodium cyanoborohydride (0.056 g, 0.81 mmol). The reaction was stirred at ambient temperature for 4 hours. The reaction was taken to dryness in vacuo, adsorbed onto silica and purified by flash chromatography on silica gel Merck-60 (eluant: 10:1 chloroform-containing 1% ammonium hydroxide) to yield the title compound (0.130 mmol, 0.19 mmol). the reaction washed with 10% sodium thiosulfate solution, water and brine The organic layer was dried with anhydrous magnesium sulfate filtered the solvent partially removed in vacuo The reaction was stirred at ambient temperature for 4 hours purified by flash chromatography on silica gel Merck-60 (eluant: 10:1 chloroform-containing 1% ammonium hydroxide)

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

Procedure: N-[4-({4-[4-(2,2-Dimethoxyethyl)anilino]-1-piperidinyl}sulfonyl)phenyl]-N′-octylurea (0.53 g, 0.92 mmol) was added to a pre-prepared mixture of sodium iodide (0.346 g, 2.31 mmol) and trichloro(methyl)silane (0.217 mL, 1.85 mmol) in anhydrous acetonitrile (27 mL). The reaction was stirred at ambient temperature for 10 minutes. Dichloromethane was added and the reaction washed with 10% sodium thiosulfate solution, water and brine. The organic layer was dried with anhydrous magnesium sulfate, filtered and the solvent partially removed in vacuo. The aldehyde solution was used directly and treated with methanol, acetic acid (0.066 mL, 1.1 mmol), N-{5-[(1R)-2-amino-1-hydroxyethyl]-2-hydroxyphenyl}methanesulfonamide (0.227 g, 0.92 mmol) followed by sodium cyanoborohydride (0.063 g, 0.92 mmol). The reaction was stirred at ambient temperature overnight. The reaction was taken to dryness in vacuo, adsorbed onto silica and purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide) to yield the title compound (0.097 g, 0.128 mmol). the reaction washed with 10% sodium thiosulfate solution, water and brine The organic layer was dried with anhydrous magnesium sulfate filtered the solvent partially removed in vacuo The reaction was stirred at ambient temperature overnight purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide)

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

Procedure: Methyl 4-({4-[4-(2,2-dimethoxyethyl)anilino]-1-piperidinyl}carbonyl)benzoate (0.30 g, 0.703 mmol) was added to a pre-prepared mixture of sodium iodide (0.264 g, 1.76 mmol) and trichloro(methyl)silane (0.166 mL, 1.4 mmol) in anhydrous acetonitrile. The reaction was stirred at ambient temperature for 10 minutes. Dichloromethane was added and the reaction washed with 10% sodium thiosulfate solution, water and brine. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvent partially removed under vacuo. The aldehyde solution was used directly and treated with methanol (17 mL), acetic acid (0.043 mL, 0.75 mmol), N-(5-[(1R)-2-amino-1-hydroxyethyl]-2-hydroxyphenyl)methanesulfonamide (0.127 g, 0.516 mmol) followed by sodium cyanoborohydride (0.048 g, 0.764 mmol). The reaction was taken to dryness in vacuo, adsorbed onto silica and purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide) to yield the title compound (0.127 g, 0.208 mmol). the reaction washed with 10% sodium thiosulfate solution, water and brine The organic layer was dried over anhydrous magnesium sulfate filtered the solvent partially removed under vacuo purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide)

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

Procedure: Ethyl 1-([4-[4-(2,2-dimethoxyethyl)anilino]-1-piperidinyl}carbonyl)-3-piperidinecarboxylate (1.0 g, 2.23 mmol) was added to a pre-prepared mixture of sodium iodide (0.893 g, 5.96 mmol) and trichloro(methyl)silane (0.561 mL, 4.77 mmol) in anhydrous acetonitrile. The reaction was stirred at ambient temperature for 10 minutes. Dichloromethane was added and the reaction washed with 10% sodium thiosulfate solution, water and brine. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvent partially removed in vacuo. The aldehyde solution was used directly and treated with methanol, acetic acid (0.156 mL, 2.6 mmol), N-{5-[(1R)-2-amino-1-hydroxyethyl]-2-hydroxyphenyl}methanesulfonamide (0.587 g, 2.38 mmol) followed by sodium cyanoborohydride (0.164 g, 2.38 mmol). The reaction was stirred at ambient temperature for 24 hours. The reaction was taken to dryness in vacuo, adsorbed onto silica and purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide) to yield the title compound (0.07 g, 0.11 mmol). the reaction washed with 10% sodium thiosulfate solution, water and brine The organic layer was dried over anhydrous magnesium sulfate filtered the solvent partially removed in vacuo The reaction was stirred at ambient temperature for 24 hours purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide)

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

Procedure: Methyl (2S)-1-({4-[4-(2,2-dimethoxyethyl)anilino]-1-piperidinyl)carbonyl)-2-pyrrolidinecarboxylate (1.0 g, 2.38 mmol) was added to a pre-prepared mixture of sodium iodide (0.837 g, 5.58 mmol) and trichloro(methyl)silane (0.525 mL, 4.46 mmol) in anhydrous acetonitrile. The reaction was stirred at ambient temperature for 10 minutes. Dichloromethane was added and the reaction washed with 10% sodium thiosulfate solution, water and brine. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvent partially removed in vacuo. The aldehyde solution was used directly and treated with methanol, acetic acid (0.146 mL, 2.43 mmol), N-{5-[(1R)-2-amino-1-hydroxyethyl]-2-hydroxyphenyl}methanesulfonamide (0.55 g, 2.23 mmol) followed by sodium cyanoborohydride (0.154 g, 2.24 mmol). The reaction was stirred at ambient temperature for 24 hours. The reaction was taken to dryness in vacuo, adsorbed onto silica and purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide) to yield the title compound (0.05 g, 0.083 mmol). the reaction washed with 10% sodium thiosulfate solution, water and brine The organic layer was dried over anhydrous magnesium sulfate filtered the solvent partially removed in vacuo The reaction was stirred at ambient temperature for 24 hours purified by flash chromatography on silica gel Merck-60 (eluant: 5:1 chloroform-methanol containing 1% ammonium hydroxide)

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

Procedure: In a 1-1 flask equipped with a dropping funnel, reflux condenser, stirrer and nitrogen gas introducing tube were placed 149 g (1 mol) of methyltrichlorosilane and 250 ml of diethyl ether. While stirring the mixture, the above chlorotrimethylsilylmethyl magnesium was dropwise added thereto over a period of 2 hours. After completion of the addition, the mixture was refluxed with heating and stirring for 36 hours. After cooling, 200 ml of hexane was added to the reaction mixture, and the salts formed were filtered off. The filtrate was condensed and vaccum-distilled. 11.7 g (yield: 43%) of (trimethylsilylmethyl)methyldichlorosilane was obtained. In a 1-1 flask equipped with a dropping funnel reflux condenser, stirrer nitrogen gas introducing tube After completion of the addition the mixture was refluxed with heating stirring for 36 hours After cooling the salts formed were filtered off condensed vaccum-distilled

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

Procedure: (2,3,4,5-Tetramethylcyclopentadienyl)lithium (1.33 g, 10.37 mmol) was dissolved in 80 mL THF and cooled to -78° C., and MeSiCl3 (1.70 g, 11.4 mmol) was added via a syringe. After addition, the cooling bath was removed and the reaction mixture was stirred at room temperature for 16 h. Volatiles were removed under vacuum at room temperature, and the residue was extracted twice with hexanes (2×20 mL). The hexane fractions were combined and the solvent was removed under vacuum to give a pale yellow oil (tetramethylcyclopentadienyl methyl silicon dichloride); 2.0 g, 82% yield. 1H-NMR (C6D6): δ(ppm): 2.95 (broad s, 1 H; Me4CpH), 1.92 (s, 6H;), 1.63 (s, 6H; Me4Cp), 0.19 (s, 3 H; MeSi). After addition the cooling bath was removed Volatiles were removed under vacuum at room temperature the residue was extracted twice with hexanes (2×20 mL) the solvent was removed under vacuum

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

Procedure: (2,3,4,5-Tetramethylcyclopentadienyl)lithium (1.33 g, 10.37 mmol) was dissolved in 80 mL THF and cooled to −78° C., and MeSiCl3 (1.70 g, 11.4 mmol) was added via a syringe. After addition, the cooling bath was removed and the reaction mixture was stirred at room temperature for 16 h. Volatiles were removed under vacuum at room temperature, and the residue was extracted twice with hexanes (2×20 mL). The hexane fractions were combined and the solvent was removed under vacuum to give a pale yellow oil (tetramethylcyclopentadienyl methyl silicon dichloride); 2.0 g, 82% yield. 1H-NMR (C6D6): δ (ppm): 2.95 (broad s, 1 H; Me4CpH), 1.92 (s, 6H;), 1.63 (s, 6H; Me4Cp), 0.19 (s, 3 H; MeSi). After addition the cooling bath was removed Volatiles were removed under vacuum at room temperature the residue was extracted twice with hexanes (2×20 mL) the solvent was removed under vacuum