1-bromo-3-(difluoromethyl)benzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1-bromo-3-(difluoromethyl)benzene (0.72 g, 3.48 mmol), tributyl(1-ethoxyvinyl)tin (1.38 g, 3.83 mmol), dichlorobis(triphenylphosphine)-palladium(II) (0.24 g, 0.35 mmol) in toluene (12 mL) is heated at 100° C. under nitrogen atmosphere for 16 hours. After cooling to room temperature, 2M hydrochloric acid (12 mL) is added to the mixture. Then the resulting mixture is stirred at room temperature for 1 hour. The mixture is diluted with ethyl acetate (100 mL) and washed with water (100 mL). The organic layer is dried over sodium sulfate, and concentrated under reduced pressure. The residue is purified by column chromatography on silica-gel eluting with n-hexane/ethyl acetate (30:1) to give 0.58 g (98% yield) of the title compound as colorless oil. After cooling to room temperature washed with water (100 mL) The organic layer is dried over sodium sulfate concentrated under reduced pressure The residue is purified by column chromatography on silica-gel eluting with n-hexane/ethyl acetate (30:1)

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1-bromo-3-(difluoromethyl)benzene (0.72 g, 3.48 mmol), tributyl(1-ethoxyvinyl)tin (1.38 g, 3.83 mmol), dichlorobis(triphenylphosphine)-palladium(II) (0.24 g, 0.35 mmol) in toluene (12 mL) is heated at 100° C. under nitrogen atmosphere for 16 hours. After cooling to room temperature, 2M hydrochloric acid (12 mL) is added to the mixture. Then the resulting mixture is stirred at room temperature for 1 hour. The mixture is diluted with ethyl acetate (100 mL) and washed with water (100 mL). The organic layer is dried over sodium sulfate, and concentrated under reduced pressure. The residue is purified by column chromatography on silica-gel eluting with n-hexane/ethyl acetate (30:1) to give 0.58 g (98% yield) of the title compound as colorless oil. After cooling to room temperature washed with water (100 mL) The organic layer is dried over sodium sulfate concentrated under reduced pressure The residue is purified by column chromatography on silica-gel eluting with n-hexane/ethyl acetate (30:1)

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

実験手順: Quantities of 1.0 g (4.83 mmol) of 3-(difluoromethyl)phenyl bromide, 1.42 g (5.31 mmol) of ethyl N-(diphenylmethylene)glycinate, 0.19 ml (0.193 mmol) of a 1M solution of tri-tert-butylphosphane in toluene, 55 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0), 3.08 g (14.49 mmol) of potassium phosphate and 6.04 ml (18.11 mmol) of 3M hydrochloric acid were heated under argon to 100° C. in 20 ml of degassed toluene, and stirred at this temperature overnight. A further 0.19 ml (0.193 mmol) of tri-tert-butylphosphane (1M solution in toluene) and 55 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0) were added and the mixture was stirred at 100° C. for a further 24 h. The mixture was cooled to RT and filtered over celite. The celite was washed with a little toluene and the filtrate was freed from the solvent under reduced pressure. For elimination of the protecting group, the residue was taken up in 50 ml of acetonitrile and admixed with 15 ml of 3M hydrochloric acid. After 2 h, the acetonitrile fraction was removed on a rotary evaporator. The aqueous residue was diluted with water to a volume of approximately 150 ml and washed three times with diethyl ether. The aqueous phase was adjusted to a pH of 9 using 2M aqueous sodium carbonate solution and then extracted three times with dichloromethane. The combined organic phases were dried over sodium sulphate, filtered and freed from the solvent on a rotary evaporator. Drying in an HV gave 265 mg (6.46% of theory) of the title compound, in a purity of about 27%, which was reacted further without additional purification. the mixture was stirred at 100° C. for a further 24 h filtered over celite The celite was washed with a little toluene After 2 h the acetonitrile fraction was removed on a rotary evaporator The aqueous residue was diluted with water to a volume of approximately 150 ml washed three times with diethyl ether extracted three times with dichloromethane The combined organic phases were dried over sodium sulphate filtered freed from the solvent on a rotary evaporator Drying in an HV

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

実験手順: Quantities of 1.0 g (4.83 mmol) of 3-(difluoromethyl)phenyl bromide, 1.42 g (5.31 mmol) of ethyl N-(diphenylmethylene)glycinate, 0.19 ml (0.193 mmol) of a 1M solution of tri-tert-butylphosphane in toluene, 55 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0), 3.08 g (14.49 mmol) of potassium phosphate and 6.04 ml (18.11 mmol) of 3M hydrochloric acid were heated under argon to 100° C. in 20 ml of degassed toluene, and stirred at this temperature overnight. A further 0.19 ml (0.193 mmol) of tri-tert-butylphosphane (1M solution in toluene) and 55 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0) were added and the mixture was stirred at 100° C. for a further 24 h. The mixture was cooled to RT and filtered over celite. The celite was washed with a little toluene and the filtrate was freed from the solvent under reduced pressure. For elimination of the protecting group, the residue was taken up in 50 ml of acetonitrile and admixed with 15 ml of 3M hydrochloric acid. After 2 h, the acetonitrile fraction was removed on a rotary evaporator. The aqueous residue was diluted with water to a volume of approximately 150 ml and washed three times with diethyl ether. The aqueous phase was adjusted to a pH of 9 using 2M aqueous sodium carbonate solution and then extracted three times with dichloromethane. The combined organic phases were dried over sodium sulphate, filtered and freed from the solvent on a rotary evaporator. Drying in an HV gave 265 mg (6.46% of theory) of the title compound, in a purity of about 27%, which was reacted further without additional purification. the mixture was stirred at 100° C. for a further 24 h filtered over celite The celite was washed with a little toluene After 2 h the acetonitrile fraction was removed on a rotary evaporator The aqueous residue was diluted with water to a volume of approximately 150 ml washed three times with diethyl ether extracted three times with dichloromethane The combined organic phases were dried over sodium sulphate filtered freed from the solvent on a rotary evaporator Drying in an HV

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: Quantities of 1.0 g (4.83 mmol) of 3-(difluoromethyl)phenyl bromide, 1.42 g (5.31 mmol) of ethyl N-(diphenylmethylene)glycinate, 0.19 ml (0.193 mmol) of a 1M solution of tri-tert-butylphosphane in toluene, 55 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0), 3.08 g (14.49 mmol) of potassium phosphate and 6.04 ml (18.11 mmol) of 3M hydrochloric acid were heated under argon to 100° C. in 20 ml of degassed toluene, and stirred at this temperature overnight. A further 0.19 ml (0.193 mmol) of tri-tert-butylphosphane (1M solution in toluene) and 55 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0) were added and the mixture was stirred at 100° C. for a further 24 h. The mixture was cooled to RT and filtered over celite. The celite was washed with a little toluene and the filtrate was freed from the solvent under reduced pressure. For elimination of the protecting group, the residue was taken up in 50 ml of acetonitrile and admixed with 15 ml of 3M hydrochloric acid. After 2 h, the acetonitrile fraction was removed on a rotary evaporator. The aqueous residue was diluted with water to a volume of approximately 150 ml and washed three times with diethyl ether. The aqueous phase was adjusted to a pH of 9 using 2M aqueous sodium carbonate solution and then extracted three times with dichloromethane. The combined organic phases were dried over sodium sulphate, filtered and freed from the solvent on a rotary evaporator. Drying in an HV gave 265 mg (6.46% of theory) of the title compound, in a purity of about 27%, which was reacted further without additional purification. the mixture was stirred at 100° C. for a further 24 h filtered over celite The celite was washed with a little toluene After 2 h the acetonitrile fraction was removed on a rotary evaporator The aqueous residue was diluted with water to a volume of approximately 150 ml washed three times with diethyl ether extracted three times with dichloromethane The combined organic phases were dried over sodium sulphate filtered freed from the solvent on a rotary evaporator Drying in an HV

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1-bromo-3-(difluoromethyl)benzene (0.72 g, 3.48 mmol), tributyl(1-ethoxyvinyl)tin (1.38 g, 3.83 mmol), dichlorobis(triphenylphosphine)-palladium(II) (0.24 g, 0.35 mmol) in toluene (12 mL) is heated at 100° C. under nitrogen atmosphere for 16 hours. After cooling to room temperature, 2M hydrochloric acid (12 mL) is added to the mixture. Then the resulting mixture is stirred at room temperature for 1 hour. The mixture is diluted with ethyl acetate (100 mL) and washed with water (100 mL). The organic layer is dried over sodium sulfate, and concentrated under reduced pressure. The residue is purified by column chromatography on silica-gel eluting with n-hexane/ethyl acetate (30:1) to give 0.58 g (98% yield) of the title compound as colorless oil. After cooling to room temperature washed with water (100 mL) The organic layer is dried over sodium sulfate concentrated under reduced pressure The residue is purified by column chromatography on silica-gel eluting with n-hexane/ethyl acetate (30:1)

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

実験手順: Quantities of 1.0 g (4.83 mmol) of 3-(difluoromethyl)phenyl bromide, 1.42 g (5.31 mmol) of ethyl N-(diphenylmethylene)glycinate, 0.19 ml (0.193 mmol) of a 1M solution of tri-tert-butylphosphane in toluene, 55 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0), 3.08 g (14.49 mmol) of potassium phosphate and 6.04 ml (18.11 mmol) of 3M hydrochloric acid were heated under argon to 100° C. in 20 ml of degassed toluene, and stirred at this temperature overnight. A further 0.19 ml (0.193 mmol) of tri-tert-butylphosphane (1M solution in toluene) and 55 mg (0.10 mmol) of bis(dibenzylideneacetone)palladium(0) were added and the mixture was stirred at 100° C. for a further 24 h. The mixture was cooled to RT and filtered over celite. The celite was washed with a little toluene and the filtrate was freed from the solvent under reduced pressure. For elimination of the protecting group, the residue was taken up in 50 ml of acetonitrile and admixed with 15 ml of 3M hydrochloric acid. After 2 h, the acetonitrile fraction was removed on a rotary evaporator. The aqueous residue was diluted with water to a volume of approximately 150 ml and washed three times with diethyl ether. The aqueous phase was adjusted to a pH of 9 using 2M aqueous sodium carbonate solution and then extracted three times with dichloromethane. The combined organic phases were dried over sodium sulphate, filtered and freed from the solvent on a rotary evaporator. Drying in an HV gave 265 mg (6.46% of theory) of the title compound, in a purity of about 27%, which was reacted further without additional purification. the mixture was stirred at 100° C. for a further 24 h filtered over celite The celite was washed with a little toluene After 2 h the acetonitrile fraction was removed on a rotary evaporator The aqueous residue was diluted with water to a volume of approximately 150 ml washed three times with diethyl ether extracted three times with dichloromethane The combined organic phases were dried over sodium sulphate filtered freed from the solvent on a rotary evaporator Drying in an HV

反応条件: temp:0.00; pressure:0.00; stir: