methyl 2,4-difluoro-3-hydroxybenzoate

反応条件: temp:0.00; pressure:0.00; stir:

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: In 20 ml of N,N-dimethylformamide was dissolved 1.00 g of methyl 2,4-difluoro-3-hydroxy-benzoate, followed by adding thereto 0.88 g of potassium carbonate and then 12 ml of a 6 M solution of chlorodifluoromethane in N,N-dimethylformamide, and the resulting mixture was stirred in a sealed tube at 120-130° C. for 2.5 hours. The reaction mixture was added to a mixed solvent of 100 ml of ethyl acetate and 200 ml of water and the pH was adjusted to 2 with 6N hydrochloric acid, after which the organic layer was separated. The organic layer obtained was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a column chromatography (eluent; n-hexane:ethyl acetate=4:1) to obtain 1.02 g of methyl 2,4-difluoro-3-difluoromethoxybenzoate as colorless crystals. by adding after which the organic layer was separated The organic layer obtained was washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent The resulting residue was purified by a column chromatography (eluent; n-hexane:ethyl acetate=4:1)

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

実験手順: In 20 ml of methylene chloride was dissolved 2.00 g of methyl 2,4-difluoro-3-methoxy-benzoate, and to the solution was added 12.8 ml of a 1 M solution of boron tribromide in methylene chloride at -30° C., after which the resulting mixture was stirred under ice-cooling for 2 hours. The reaction mixture was added to a mixed solvent of 150 ml of ethyl acetate and 150 ml of water and the organic layer was separated. The organic layer obtained was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a column chromatography (eluent; n-exane:ethyl acetate=3:1) to obtain 1.35 g of methyl 2,4-difluoro-3-hydroxybenzoate as colorless crystals. cooling for 2 hours the organic layer was separated The organic layer obtained was washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent The resulting residue was purified by a column chromatography (eluent; n-exane:ethyl acetate=3:1)

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

実験手順: In 20 ml of N,N-dimethylformamide was dissolved 1.00 g of methyl 2,4-difluoro-3-hydroxy-benzoate, followed by adding thereto 0.88 g of potassium carbonate and then 12 ml of a 6 M solution of chlorodifluoromethane in N,N-dimethylformamide, and the resulting mixture was stirred in a sealed tube at 120-130° C. for 2.5 hours. The reaction mixture was added to a mixed solvent of 100 ml of ethyl acetate and 200 ml of water and the pH was adjusted to 2 with 6N hydrochloric acid, after which the organic layer was separated. The organic layer obtained was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a column chromatography (eluent; n-hexane:ethyl acetate=4:1) to obtain 1.02 g of methyl 2,4-difluoro-3-difluoromethoxybenzoate as colorless crystals. by adding after which the organic layer was separated The organic layer obtained was washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent The resulting residue was purified by a column chromatography (eluent; n-hexane:ethyl acetate=4:1)

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

実験手順: In 20 ml of N,N-dimethylformamide was dissolved 1.00 g of methyl 2,4-difluoro-3-hydroxy-benzoate, followed by adding thereto 0.88 g of potassium carbonate and then 12 ml of a 6 M solution of chlorodifluoromethane in N,N-dimethylformamide, and the resulting mixture was stirred in a sealed tube at 120-130° C. for 2.5 hours. The reaction mixture was added to a mixed solvent of 100 ml of ethyl acetate and 200 ml of water and the pH was adjusted to 2 with 6N hydrochloric acid, after which the organic layer was separated. The organic layer obtained was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a column chromatography (eluent; n-hexane:ethyl acetate=4:1) to obtain 1.02 g of methyl 2,4-difluoro-3-difluoromethoxybenzoate as colorless crystals. by adding after which the organic layer was separated The organic layer obtained was washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent The resulting residue was purified by a column chromatography (eluent; n-hexane:ethyl acetate=4:1)

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

実験手順: In 20 ml of methylene chloride was dissolved 2.00 g of methyl 2,4-difluoro-3-methoxy-benzoate, and to the solution was added 12.8 ml of a 1 M solution of boron tribromide in methylene chloride at -30° C., after which the resulting mixture was stirred under ice-cooling for 2 hours. The reaction mixture was added to a mixed solvent of 150 ml of ethyl acetate and 150 ml of water and the organic layer was separated. The organic layer obtained was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a column chromatography (eluent; n-exane:ethyl acetate=3:1) to obtain 1.35 g of methyl 2,4-difluoro-3-hydroxybenzoate as colorless crystals. cooling for 2 hours the organic layer was separated The organic layer obtained was washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent The resulting residue was purified by a column chromatography (eluent; n-exane:ethyl acetate=3:1)

反応条件: temp:0.00; pressure:0.00; stir:

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: In 20 ml of N,N-dimethylformamide was dissolved 1.00 g of methyl 2,4-difluoro-3-hydroxy-benzoate, followed by adding thereto 0.88 g of potassium carbonate and then 12 ml of a 6 M solution of chlorodifluoromethane in N,N-dimethylformamide, and the resulting mixture was stirred in a sealed tube at 120-130° C. for 2.5 hours. The reaction mixture was added to a mixed solvent of 100 ml of ethyl acetate and 200 ml of water and the pH was adjusted to 2 with 6N hydrochloric acid, after which the organic layer was separated. The organic layer obtained was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a column chromatography (eluent; n-hexane:ethyl acetate=4:1) to obtain 1.02 g of methyl 2,4-difluoro-3-difluoromethoxybenzoate as colorless crystals. by adding after which the organic layer was separated The organic layer obtained was washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent The resulting residue was purified by a column chromatography (eluent; n-hexane:ethyl acetate=4:1)

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

実験手順: In 20 ml of methylene chloride was dissolved 2.00 g of methyl 2,4-difluoro-3-methoxy-benzoate, and to the solution was added 12.8 ml of a 1 M solution of boron tribromide in methylene chloride at -30° C., after which the resulting mixture was stirred under ice-cooling for 2 hours. The reaction mixture was added to a mixed solvent of 150 ml of ethyl acetate and 150 ml of water and the organic layer was separated. The organic layer obtained was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a column chromatography (eluent; n-exane:ethyl acetate=3:1) to obtain 1.35 g of methyl 2,4-difluoro-3-hydroxybenzoate as colorless crystals. cooling for 2 hours the organic layer was separated The organic layer obtained was washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent The resulting residue was purified by a column chromatography (eluent; n-exane:ethyl acetate=3:1)