methyl 5-amino-2-bromobenzoate

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:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-bromophenyl boronic acid (600 mg, 3.0 mmol), methyl 5-amino-2-bromobenzoate (1.5 g, 6.5 mmol), potassium carbonate (2.07 g, 15 mmol) and tetrakis(triphenylphosphine)palladium (0) (345 mg, 5 mol %) in 1:1 toluene/ethanol (20 ml) was stirred and heated at 90° C. under nitrogen for 12 hours. After cooling the mixture was diluted with diethyl ether and water and the organic phase dried (MgSO4) and evaporated to dryness. The residue was chromatographed with dichloromethane/iso-hexane (1:2->1:1) to yield the title compound as a pale yellow gum. (682 mg, 74%). After cooling the mixture the organic phase dried (MgSO4) evaporated to dryness The residue was chromatographed with dichloromethane/iso-hexane (1:2->1:1)

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-bromophenyl boronic acid (600 mg, 3.0 mmol), methyl 5-amino-2-bromobenzoate (1.5 g, 6.5 mmol), potassium carbonate (2.07 g, 15 mmol) and tetrakis(triphenylphosphine)palladium (0) (345 mg, 5 mol %) in 1:1 toluene/ethanol (20 ml) was stirred and heated at 90° C. under nitrogen for 12 hours. After cooling the mixture was diluted with diethyl ether and water and the organic phase dried (MgSO4) and evaporated to dryness. The residue was chromatographed with dichloromethane/iso-hexane (1:2->1:1) to yield the title compound as a pale yellow gum. (682 mg, 74%). After cooling the mixture the organic phase dried (MgSO4) evaporated to dryness The residue was chromatographed with dichloromethane/iso-hexane (1:2->1:1)

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

実験手順: Methyl 2-bromo-5-nitrobenzoate (25.3 g, 97.3 mmol) was dissolved in anhydrous methanol (500 mL), Tin (II) chloride (93.3 g, 487 mmol) was added thereto, and then the reaction mixture was refluxed for 2 hours. The reaction mixture was cooled down, ethyl acetate (500 mL) and water (100 mL) were added thereto, the mixture was neutralized with 4N aqueous sodium hydroxide solution, and then filtered on celite. The filtrate was concentrated under reduced pressure, ethyl acetate (200 mL) was added thereto, and then the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (200 mL, 2 times), water (200 mL), and saturated brine (200 mL) successively. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the titled reference compound (21.0 g) as a pale yellow oil. (Yield 94%) the reaction mixture was refluxed for 2 hours The reaction mixture was cooled down filtered on celite The filtrate was concentrated under reduced pressure, ethyl acetate (200 mL) was added the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (200 mL, 2 times), water (200 mL), and saturated brine (200 mL) successively The organic layer was dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure

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

実験手順: Methyl 2-Bromo-5-nitrobenzoate (25.3 g 97.3 mmol) was dissolved in anhydrous methanol (50 mL), and tin (II) chloride (93.3 g, 487 mmol) was added thereto, and then the reaction mixture was refluxed for 2 hours. After cooling down, ethyl acetate (500 mL) and water (100 mL) were added thereto, and the mixture was neutralized with 4N aqueous NaOH solution, and then it was filtered on celite. The filtrate was concentrated under reduced pressure, and ethyl acetate (200 mL) was added thereto, and then it was washed with saturated NaHCO3 solution (200 mL, twice), water (200 mL) and saturated brine (200 mL) successively. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the titled reference compound (21.0 g) as a yellow oil. (Yield 94%) the reaction mixture was refluxed for 2 hours After cooling down it was filtered on celite The filtrate was concentrated under reduced pressure, and ethyl acetate (200 mL) was added it was washed with saturated NaHCO3 solution (200 mL The organic layer was dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure

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

実験手順: Methyl 2-Bromo-5-nitrobenzoate (25.3 g 97.3 mmol) was dissolved in anhydrous methanol (50 mL), and tin (II) chloride (93.3 g, 487 mmol) was added thereto, and then the reaction mixture was refluxed for 2 hours. After cooling down, ethyl acetate (500 mL) and water (100 mL) were added thereto, and the mixture was neutralized with 4N aqueous NaOH solution, and then it was filtered on celite. The filtrate was concentrated under reduced pressure, and ethyl acetate (200 mL) was added thereto, and then it was washed with saturated NaHCO3 solution (200 mL, twice), water (200 mL) and saturated brine (200 mL) successively. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the titled reference compound (21.0 g) as a yellow oil. (Yield 94%) the reaction mixture was refluxed for 2 hours After cooling down it was filtered on celite The filtrate was concentrated under reduced pressure, and ethyl acetate (200 mL) was added it was washed with saturated NaHCO3 solution (200 mL The organic layer was dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure

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

実験手順: Methyl 5-amino-2-bromobenzoate (Reference Compound No. 1-(1), 21.0 g, 91.2 mmol) was dissolved in anhydrous dichloromethane (450 mL), triethylamine (19.0 mL, 137 mmol) and acetyl chloride (13.0 mL, 182 mmol) were added dropwise over 30 minutes successively, and then the mixture was stirred at 0° C. for 2 hours. The reaction mixture was washed with water (200 mL, 2 times), saturated aqueous sodium hydrogen carbonate solution (200 mL, 2 times), and saturated brine (200 mL) successively, dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was filtered with hexane-ethyl acetate (20:1) to give the titled reference compound (24.2 g) as a pale yellow solid. (Yield 98%) The reaction mixture was washed with water (200 mL, 2 times), saturated aqueous sodium hydrogen carbonate solution (200 mL, 2 times), and saturated brine (200 mL) successively dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The obtained residue was filtered with hexane-ethyl acetate (20:1)

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

実験手順: Methyl 5-amino-2-bromobenzoate (Reference Compound No. 1-(1), 21.0 g, 91.2 mmol) was dissolved in anhydrous dichloromethane (450 mL), triethylamine (19.0 mL, 137 mmol) and acetyl chloride (13.0 mL, 182 mmol) were added dropwise over 30 minutes successively, and then the mixture was stirred at 0° C. for 2 hours. The reaction mixture was washed with water (200 mL, 2 times), saturated aqueous sodium hydrogen carbonate solution (200 mL, 2 times), and saturated brine (200 mL) successively, dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was filtered with hexane-ethyl acetate (20:1) to give the titled reference compound (24.2 g) as a pale yellow solid. (Yield 98%) The reaction mixture was washed with water (200 mL, 2 times), saturated aqueous sodium hydrogen carbonate solution (200 mL, 2 times), and saturated brine (200 mL) successively dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The obtained residue was filtered with hexane-ethyl acetate (20:1)

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

実験手順: Methyl 2-bromo-5-nitrobenzoate (25.3 g, 97.3 mmol) was dissolved in anhydrous methanol (500 mL), Tin (II) chloride (93.3 g, 487 mmol) was added thereto, and then the reaction mixture was refluxed for 2 hours. The reaction mixture was cooled down, ethyl acetate (500 mL) and water (100 mL) were added thereto, the mixture was neutralized with 4N aqueous sodium hydroxide solution, and then filtered on celite. The filtrate was concentrated under reduced pressure, ethyl acetate (200 mL) was added thereto, and then the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (200 mL, 2 times), water (200 mL), and saturated brine (200 mL) successively. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the titled reference compound (21.0 g) as a pale yellow oil. (Yield 94%) the reaction mixture was refluxed for 2 hours The reaction mixture was cooled down filtered on celite The filtrate was concentrated under reduced pressure, ethyl acetate (200 mL) was added the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (200 mL, 2 times), water (200 mL), and saturated brine (200 mL) successively The organic layer was dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-bromophenyl boronic acid (600 mg, 3.0 mmol), methyl 5-amino-2-bromobenzoate (1.5 g, 6.5 mmol), potassium carbonate (2.07 g, 15 mmol) and tetrakis(triphenylphosphine)palladium (0) (345 mg, 5 mol %) in 1:1 toluene/ethanol (20 ml) was stirred and heated at 90° C. under nitrogen for 12 hours. After cooling the mixture was diluted with diethyl ether and water and the organic phase dried (MgSO4) and evaporated to dryness. The residue was chromatographed with dichloromethane/iso-hexane (1:2->1:1) to yield the title compound as a pale yellow gum. (682 mg, 74%). After cooling the mixture the organic phase dried (MgSO4) evaporated to dryness The residue was chromatographed with dichloromethane/iso-hexane (1:2->1:1)

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

実験手順: Methyl 5-amino-2-bromobenzoate (Reference Compound No. 1-(1), 21.0 g, 91.2 mmol) and triethylamine (19.0 mL, 137 mmol) were dissolved in anhydrous dichloromethane (450 mL), acetyl chloride (13.0 mL, 182 mmol) was added dropwise over 30 minutes under ice cooling, and then the mixture was stirred at 0° C. for 2 hours. The reaction mixture was washed with water (200 mL, twice), saturated aqueous sodium hydrogen carbonate solution (200 mL, twice), and saturated brine (200 mL) successively, dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was filtered with hexane-ethyl acetate (20:1) to give the titled reference compound (24.2 g) as a pale yellow solid. (Yield 98%) The reaction mixture was washed with water (200 mL twice), saturated aqueous sodium hydrogen carbonate solution (200 mL, twice), and saturated brine (200 mL) successively, dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The obtained residue was filtered with hexane-ethyl acetate (20:1)