ethyl 4-bromo-3,5-dihydroxybenzoate

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: To a solution of 17.8 g (67.9 mmol) of triphenylphosphane, 8.8 ml (67.9 mmol) of 2-(2,4-dichlorophenyl)ethanol and 16 g (61.3 mmol) of 4-bromo-3,5-dihydroxybenzoic acid ethyl ester in 25 ml of THF was added a solution of 10.6 ml (67.9 mmol) of DEAD in 40 ml of THF within 45 min between 620 and 18° C. After 16 h at room temperature the solvent was removed and the residue was stirred with cyclohexane/ethyl acetate (1/1) and filtered. The solid residue was stirred with cyclohexane and filtered. The remaining solid was separated by chromatography (cyclohexane/ethyl acetate (1/1)) to give 25.6 g (96%) of the title compound. After 16 h at room temperature the solvent was removed filtered The solid residue was stirred with cyclohexane filtered The remaining solid was separated by chromatography (cyclohexane/ethyl acetate (1/1))

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

実験手順: To a solution of 17.8 g (67.9 mmol) of triphenylphosphane, 8.8 ml (67.9 mmol) of 2-(2,4-dichlorophenyl)ethanol and 16 g (61.3 mmol) of 4-bromo-3,5-dihydroxybenzoic acid ethyl ester in 25 ml of THF was added a solution of 10.6 ml (67.9 mmol) of DEAD in 40 ml of THF within 45 min between 620 and 18° C. After 16 h at room temperature the solvent was removed and the residue was stirred with cyclohexane/ethyl acetate (1/1) and filtered. The solid residue was stirred with cyclohexane and filtered. The remaining solid was separated by chromatography (cyclohexane/ethyl acetate (1/1)) to give 25.6 g (96%) of the title compound. After 16 h at room temperature the solvent was removed filtered The solid residue was stirred with cyclohexane filtered The remaining solid was separated by chromatography (cyclohexane/ethyl acetate (1/1))

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

実験手順: Sodium hydride (60% oil, 10.1 g) was added to a mixture of ethyl 4-bromo-3,5-dihydroxybenzoate (30.0 g) and DMF (200 mL), and the resultant mixture was stirred at 0° C. for 30 minutes in a nitrogen atmosphere. 1-Iodopropane (11.2 mL) was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain the title compound (14.1 g). followed by extraction with ethyl acetate The obtained organic layer was washed with saturated saline dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate)

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

実験手順: Sodium hydride (60% oil, 10.1 g) was added to a mixture of ethyl 4-bromo-3,5-dihydroxybenzoate (30.0 g) and DMF (200 mL), and the resultant mixture was stirred at 0° C. for 30 minutes in a nitrogen atmosphere. 1-Iodopropane (11.2 mL) was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain the title compound (14.1 g). followed by extraction with ethyl acetate The obtained organic layer was washed with saturated saline dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate)

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

実験手順: A mixture of 4-bromo-3,5-dihydroxybenzoic acid (45.0 g), concentrated sulfuric acid (5 mL), and ethanol (300 mL) was heated to reflux for 24 hours. The solvent was distilled off under reduced pressure. The residue was diluted with ethyl acetate and washed with water, a saturated aqueous solution of sodium bicarbonate, and saturated saline in this order. The obtained organic layer was dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained solid was washed with hexane to obtain the title compound (48.3 g). was heated to reflux for 24 hours The solvent was distilled off under reduced pressure The residue was diluted with ethyl acetate washed with water The obtained organic layer was dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure The obtained solid was washed with hexane

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

実験手順: Sodium hydride (60% oil, 3.86 g) was added to a DMF (100 mL) solution of ethyl 4-bromo-3,5-dihydroxybenzoate (12.3 g), and the mixture was stirred at 00° C. for 30 minutes in a nitrogen atmosphere. Iodoethane (4.15 mL) was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain the title compound (8.87 g). the mixture was stirred at room temperature for 2 hours followed by extraction with ethyl acetate The obtained organic layer was washed with saturated saline dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate)

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

実験手順: To a solution of 17.8 g (67.9 mmol) of triphenylphosphane, 8.8 ml (67.9 mmol) of 2-(2,4-dichlorophenyl)ethanol and 16 g (61.3 mmol) of 4-bromo-3,5-dihydroxybenzoic acid ethyl ester in 25 ml of THF was added a solution of 10.6 ml (67.9 mmol) of DEAD in 40 ml of THF within 45 min between 6° and 18° C. After 16 h at room temperature the solvent was removed and the residue was stirred with cyclohexane/ethyl acetate (1/1) and filtered. The solid residue was stirred with cyclohexane and filtered. The remaining solid was separated by chromatography (cyclohexane/ethyl acetate (1/1)) to give 25.6 g (96%) of the title compound. After 16 h at room temperature the solvent was removed filtered The solid residue was stirred with cyclohexane filtered The remaining solid was separated by chromatography (cyclohexane/ethyl acetate (1/1))

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

実験手順: To a solution of 17.8 g (67.9 mmol) of triphenylphosphane, 8.8 ml (67.9 mmol) of 2-(2,4-dichlorophenyl)ethanol and 16 g (61.3 mmol) of 4-bromo-3,5-dihydroxybenzoic acid ethyl ester in 25 ml of THF was added a solution of 10.6 ml (67.9 mmol) of DEAD in 40 ml of THF within 45 min between 6° and 18° C. After 16 h at room temperature the solvent was removed and the residue was stirred with cyclohexane/ethyl acetate (1/1) and filtered. The solid residue was stirred with cyclohexane and filtered. The remaining solid was separated by chromatography (cyclohexane/ethyl acetate (1/1)) to give 25.6 g (96%) of the title compound. After 16 h at room temperature the solvent was removed filtered The solid residue was stirred with cyclohexane filtered The remaining solid was separated by chromatography (cyclohexane/ethyl acetate (1/1))

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: Sodium hydride (60% oil, 10.1 g) was added to a mixture of ethyl 4-bromo-3,5-dihydroxybenzoate (30.0 g) and DMF (200 mL), and the resultant mixture was stirred at 0° C. for 30 minutes in a nitrogen atmosphere. 1-Iodopropane (11.2 mL) was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain the title compound (14.1 g). followed by extraction with ethyl acetate The obtained organic layer was washed with saturated saline dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate)

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

実験手順: A mixture of 4-bromo-3,5-dihydroxybenzoic acid (45.0 g), concentrated sulfuric acid (5 mL), and ethanol (300 mL) was heated to reflux for 24 hours. The solvent was distilled off under reduced pressure. The residue was diluted with ethyl acetate and washed with water, a saturated aqueous solution of sodium bicarbonate, and saturated saline in this order. The obtained organic layer was dried over anhydrous magnesium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained solid was washed with hexane to obtain the title compound (48.3 g). was heated to reflux for 24 hours The solvent was distilled off under reduced pressure The residue was diluted with ethyl acetate washed with water The obtained organic layer was dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure The obtained solid was washed with hexane