甲基 3-(2-氯-6-氟苯基)-3-氧代丙酸乙酯

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 5.80 g (25.1 mmol) of methyl 3-(2-chloro-6-fluorophenyl)-3-oxopropionate in 60 mL acetonitrile was added 3.9 mL (28 mmol) of triethylamine followed by 3.05 g (25.2 mmol) of methanesulfonyl azide. The mixture was stirred at room temperature for 18 h and concentrated by rotary evaporation. The resulting solid mass was washed with ethyl acetate/hexanes and the washings were filtered through a plug of silica gel. The filtrate was concentrated to give 4.90 g (76%) of the title compound as a light yellow solid. concentrated by rotary evaporation The resulting solid mass was washed with ethyl acetate/hexanes the washings were filtered through a plug of silica gel The filtrate was concentrated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 7.4 g (77.7 mmol) of magnesium chloride and 9.02 g (116.1 mmol) of methyl acetoacetate was added 30 mL acetonitrile. The mixture was cooled in an ice bath and 12.6 mL (155.4 mmol) of pyridine was slowly added while keeping the temperature below 5° C. The reaction was removed from the ice bath and was stirred for 30 min. at room temperature. A solution of 15.0 g (77.7 mmol) 2-chloro-6-fluorobenzoyl chloride in 20 mL toluene was added to the reaction and the mixture was subsequently refluxed for four hours. The reaction was then cooled to room temperature and carefully treated with 6.5 mL (98.1 mmol) of concentrated sulfuric acid. The reaction was diluted with water and the layers were separated. The aqueous layer was extracted with dichloromethane and the combined organic layers were dried over sodium sulfate and concentrated to a residue. The residue was purified by flash chromatography eluting with 15% ethyl acetate/hexanes mixture to give 14.0 g (78%) of the title compound as a reddish-pink oil. The mixture was cooled in an ice bath the temperature below 5° C The reaction was removed from the ice bath the mixture was subsequently refluxed for four hours The reaction was then cooled to room temperature the layers were separated The aqueous layer was extracted with dichloromethane the combined organic layers were dried over sodium sulfate concentrated to a residue The residue was purified by flash chromatography eluting with 15% ethyl acetate/hexanes mixture

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 7.4 g (77.7 mmol) of magnesium chloride and 9.02 g (116.1 mmol) of methyl acetoacetate was added 30 mL acetonitrile. The mixture was cooled in an ice bath and 12.6 mL (155.4 mmol) of pyridine was slowly added while keeping the temperature below 5° C. The reaction was removed from the ice bath and was stirred for 30 min. at room temperature. A solution of 15.0 g (77.7 mmol) 2-chloro-6-fluorobenzoyl chloride in 20 mL toluene was added to the reaction and the mixture was subsequently refluxed for four hours. The reaction was then cooled to room temperature and carefully treated with 6.5 mL (98.1 mmol) of concentrated sulfuric acid. The reaction was diluted with water and the layers were separated. The aqueous layer was extracted with dichloromethane and the combined organic layers were dried over sodium sulfate and concentrated to a residue. The residue was purified by flash chromatography eluting with 15% ethyl acetate/hexanes mixture to give 14.0 g (78%) of the title compound as a reddish-pink oil. The mixture was cooled in an ice bath the temperature below 5° C The reaction was removed from the ice bath the mixture was subsequently refluxed for four hours The reaction was then cooled to room temperature the layers were separated The aqueous layer was extracted with dichloromethane the combined organic layers were dried over sodium sulfate concentrated to a residue The residue was purified by flash chromatography eluting with 15% ethyl acetate/hexanes mixture

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 5.80 g (25.1 mmol) of methyl 3-(2-chloro-6-fluorophenyl)-3-oxopropionate in 60 mL acetonitrile was added 3.9 mL (28 mmol) of triethylamine followed by 3.05 g (25.2 mmol) of methanesulfonyl azide. The mixture was stirred at room temperature for 18 h and concentrated by rotary evaporation. The resulting solid mass was washed with ethyl acetate/hexanes and the washings were filtered through a plug of silica gel. The filtrate was concentrated to give 4.90 g (76%) of the title compound as a light yellow solid. concentrated by rotary evaporation The resulting solid mass was washed with ethyl acetate/hexanes the washings were filtered through a plug of silica gel The filtrate was concentrated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 7.4 g (77.7 mmol) of magnesium chloride and 9.02 g (116.1 mmol) of methyl acetoacetate was added 30 mL acetonitrile. The mixture was cooled in an ice bath and 12.6 mL (155.4 mmol) of pyridine was slowly added while keeping the temperature below 5° C. The reaction was removed from the ice bath and was stirred for 30 min. at room temperature. A solution of 15.0 g (77.7 mmol) 2-chloro-6-fluorobenzoyl chloride in 20 mL toluene was added to the reaction and the mixture was subsequently refluxed for four hours. The reaction was then cooled to room temperature and carefully treated with 6.5 mL (98.1 mmol) of concentrated sulfuric acid. The reaction was diluted with water and the layers were separated. The aqueous layer was extracted with dichloromethane and the combined organic layers were dried over sodium sulfate and concentrated to a residue. The residue was purified by flash chromatography eluting with 15% ethyl acetate/hexanes mixture to give 14.0 g (78%) of the title compound as a reddish-pink oil. The mixture was cooled in an ice bath the temperature below 5° C The reaction was removed from the ice bath the mixture was subsequently refluxed for four hours The reaction was then cooled to room temperature the layers were separated The aqueous layer was extracted with dichloromethane the combined organic layers were dried over sodium sulfate concentrated to a residue The residue was purified by flash chromatography eluting with 15% ethyl acetate/hexanes mixture