ethyl 2,6-difluorobenzoate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:50.01; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of ethyl-2,6-difluorobenzene-carboxylate (EXAMPLE 1C; 373 mg, 2.0 mmol) in DMSO (0.5 ml) was added to a solution of the solid prepared above in DMSO (1.0 ml). The brownish solution was heated at 80° C. for 2 hours. The solvent was evaporated, the solid filtered, washed with water several times and dried. The crude product was purified by flash column chromatography on silica gel using 3-15% ethyl acetate in hexane to give 371 mg of the product (61% yield) as a light yellow oil and unreacted sesamol. The solvent was evaporated the solid filtered washed with water several times dried The crude product was purified by flash column chromatography on silica gel using 3-15% ethyl acetate in hexane

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Ethyl 2,6-difluorobenzoate (558 mg, 3.0 mmol) was added to dry sodium 3,4-methylenedioxyphenoxide (3.0 mmol, prepared as described in part A) in DMSO followed by addition of dry DMSO (2 ml). The reaction mixture was warmed to 50° C. forming a solution which turned from brown to green upon further heating. After 90 min., the reaction was cooled to 25° C., diluted with water (10 ml) and extracted with EtOAc (3×10 ml). The organic extract was washed with water (2×7 ml) and brine (7 ml), dried (MgSO4) and concentrated to give a light yellow oil. The product was purified by flash chromatography on SiO2 (5-20% EtOAc/hexane) yielding 532 mg of ethyl 2-fluoro-6-[3,4-(methylenedioxy)phenoxy]benzoate as a colorless oil (58% yield). prepared forming a solution which the reaction was cooled to 25° C. extracted with EtOAc (3×10 ml) The organic extract was washed with water (2×7 ml) and brine (7 ml) dried (MgSO4) concentrated to give a light yellow oil The product was purified by flash chromatography on SiO2 (5-20% EtOAc/hexane)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Difluorobenzoyl chloride was diluted with CH2Cl2 (5 ml) and cooled to 0° C. A mixture of EtOH (1.2 ml, 20 mmol) and pyridine (1.6 ml, 20 mmol) was added, dropwise, over 5 minutes to the reaction mixture. The ice bath was removed after 5 minutes and the reaction mixture strirred at 25° C. for 45 min. The solvent and volatiles were evaporated under reduced pressure and the residue was partitioned between 1N HCl and EtOAc (10 ml each). The aqueous phase was separated and extracted with 2×7 ml EtOAc. The combined organic extracts was washed with NaHCO3 (10 ml), brine (7 ml), dried over MgSO4 and concentrated to give 1.562 g ethyl 2,6-difluorobenzoate as an almost colorless oil. (84% yield from steps B and C). was added The ice bath was removed after 5 minutes the reaction mixture strirred at 25° C. for 45 min The solvent and volatiles were evaporated under reduced pressure the residue was partitioned between 1N HCl and EtOAc (10 ml each) The aqueous phase was separated extracted with 2×7 ml EtOAc The combined organic extracts was washed with NaHCO3 (10 ml), brine (7 ml) dried over MgSO4 concentrated

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of ethyl-2,6-difluorobenzene-carboxylate (EXAMPLE 1C; 373 mg, 2.0 mmol) in DMSO (0.5 ml) was added to a solution of the solid prepared above in DMSO (1.0 ml). The brownish solution was heated at 80° C. for 2 hours. The solvent was evaporated, the solid filtered, washed with water several times and dried. The crude product was purified by flash column chromatography on silica gel using 3-15% ethyl acetate in hexane to give 371 mg of the product (61% yield) as a light yellow oil and unreacted sesamol. The solvent was evaporated the solid filtered washed with water several times dried The crude product was purified by flash column chromatography on silica gel using 3-15% ethyl acetate in hexane

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Ethyl 2,6-difluorobenzoate (558 mg, 3.0 mmol) was added to dry sodium 3,4-methylenedioxyphenoxide (3.0 mmol, prepared as described in part A) in DMSO followed by addition of dry DMSO (2 ml). The reaction mixture was warmed to 50° C. forming a solution which turned from brown to green upon further heating. After 90 min., the reaction was cooled to 25° C., diluted with water (10 ml) and extracted with EtOAc (3×10 ml). The organic extract was washed with water (2×7 ml) and brine (7 ml), dried (MgSO4) and concentrated to give a light yellow oil. The product was purified by flash chromatography on SiO2 (5-20% EtOAc/hexane) yielding 532 mg of ethyl 2-fluoro-6-[3,4-(methylenedioxy)phenoxy]benzoate as a colorless oil (58% yield). prepared forming a solution which the reaction was cooled to 25° C. extracted with EtOAc (3×10 ml) The organic extract was washed with water (2×7 ml) and brine (7 ml) dried (MgSO4) concentrated to give a light yellow oil The product was purified by flash chromatography on SiO2 (5-20% EtOAc/hexane)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Difluorobenzoyl chloride was diluted with CH2Cl2 (5 ml) and cooled to 0° C. A mixture of EtOH (1.2 ml, 20 mmol) and pyridine (1.6 ml, 20 mmol) was added, dropwise, over 5 minutes to the reaction mixture. The ice bath was removed after 5 minutes and the reaction mixture stirred at 25° C. for 45 min. The solvent and volatiles were evaporated under reduced pressure and the residue was partitioned between 1N HCl and EtOAc (10 ml each). The aqueous phase was separated and extracted with 2×7 ml EtOAc. The combined organic extracts was washed with NaHCO3 (10 ml), brine (7 ml), dried over MgSO4 and concentrated to give 1.562 g ethyl 2,6-difluorobenzoate as an almost colorless oil. (84% yield from steps B and C). was added The ice bath was removed after 5 minutes The solvent and volatiles were evaporated under reduced pressure the residue was partitioned between 1N HCl and EtOAc (10 ml each) The aqueous phase was separated extracted with 2×7 ml EtOAc The combined organic extracts was washed with NaHCO3 (10 ml), brine (7 ml) dried over MgSO4 concentrated