tert-butyl 4-amino-2-methylbenzoate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound (135 mg, 0.289 mmol) obtained in Example 4g and the compound (103 mg, 0.473 mmol) obtained in Example 18a were dissolved in methylene chloride (4 mL), acetic acid (73 μL) and sodium triacetoxyborohydride (137 mg, 0.645 mmol) were added, and the mixture was stirred overnight at room temperature. Sodium borohydride (16 mg, 0.430 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. The solvent was evaporated under reduced pressure, and the resulting residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1→1:2, v/v) to give the title compound (114 mg; yield, 40%) as a white solid. the mixture was stirred at room temperature for 20 minutes The solvent was evaporated under reduced pressure the resulting residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1→1:2, v/v)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound (135 mg, 0.289 mmol) obtained in Example 4g and the compound (103 mg, 0.473 mmol) obtained in Example 18a were dissolved in methylene chloride (4 mL), acetic acid (73 μL) and sodium triacetoxyborohydride (137 mg, 0.645 mmol) were added, and the mixture was stirred overnight at room temperature. Sodium borohydride (16 mg, 0.430 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. The solvent was evaporated under reduced pressure, and the resulting residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1→1:2, v/v) to give the title compound (114 mg; yield, 40%) as a white solid. the mixture was stirred at room temperature for 20 minutes The solvent was evaporated under reduced pressure the resulting residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1→1:2, v/v)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Methyl-4-nitrobenzoic acid (700 mg, 3.86 mmol) was dissolved in pyridine (8 mL), p-toluenesulfonyl chloride (1.47 g, 7.74 mmol) was added, then tert-butanol (0.369 mL, 3.86 mmol) was added under ice cooling, and the mixture was stirred at 0° C. for 2 hours and at room temperature for 2 hours. tert-Butanol (0.369 mL, 3.86 mmol) was further added, and the mixture was stirred overnight at room temperature. The solvent was evaporated under reduced pressure, water was added, then the mixture was extracted with ethyl acetate (×3), and the organic layer was washed with 1 N hydrochloric acid, a 1 N aqueous sodium hydroxide solution, water, and saturated sodium chloride solution. The organic layer was dried with anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, a solution of the resulting residue in ethyl acetate (40 mL) was added to 10% palladium-carbon (dry; 222 mg), the atmosphere in the system was replaced with a hydrogen atmosphere, and then the mixture was stirred at room temperature for 2 hours. The atmosphere in the system was replaced with a nitrogen atmosphere, and then the mixture was filtered through celite. The solvent was evaporated under reduced pressure to give the title compound (835 mg; yield, 100%) as a brown solid. the mixture was stirred overnight at room temperature The solvent was evaporated under reduced pressure, water was added the mixture was extracted with ethyl acetate (×3) the organic layer was washed with 1 N hydrochloric acid The organic layer was dried with anhydrous sodium sulfate the solvent was evaporated under reduced pressure a solution of the resulting residue in ethyl acetate (40 mL) was added to 10% palladium-carbon (dry; 222 mg) the mixture was stirred at room temperature for 2 hours the mixture was filtered through celite The solvent was evaporated under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The compound (135 mg, 0.289 mmol) obtained in Example 4g and the compound (103 mg, 0.473 mmol) obtained in Example 18a were dissolved in methylene chloride (4 mL), acetic acid (73 μL) and sodium triacetoxyborohydride (137 mg, 0.645 mmol) were added, and the mixture was stirred overnight at room temperature. Sodium borohydride (16 mg, 0.430 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. The solvent was evaporated under reduced pressure, and the resulting residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1→1:2, v/v) to give the title compound (114 mg; yield, 40%) as a white solid. the mixture was stirred at room temperature for 20 minutes The solvent was evaporated under reduced pressure the resulting residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1→1:2, v/v)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Methyl-4-nitrobenzoic acid (700 mg, 3.86 mmol) was dissolved in pyridine (8 mL), p-toluenesulfonyl chloride (1.47 g, 7.74 mmol) was added, then tert-butanol (0.369 mL, 3.86 mmol) was added under ice cooling, and the mixture was stirred at 0° C. for 2 hours and at room temperature for 2 hours. tert-Butanol (0.369 mL, 3.86 mmol) was further added, and the mixture was stirred overnight at room temperature. The solvent was evaporated under reduced pressure, water was added, then the mixture was extracted with ethyl acetate (×3), and the organic layer was washed with 1 N hydrochloric acid, a 1 N aqueous sodium hydroxide solution, water, and saturated sodium chloride solution. The organic layer was dried with anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, a solution of the resulting residue in ethyl acetate (40 mL) was added to 10% palladium-carbon (dry; 222 mg), the atmosphere in the system was replaced with a hydrogen atmosphere, and then the mixture was stirred at room temperature for 2 hours. The atmosphere in the system was replaced with a nitrogen atmosphere, and then the mixture was filtered through celite. The solvent was evaporated under reduced pressure to give the title compound (835 mg; yield, 100%) as a brown solid. the mixture was stirred overnight at room temperature The solvent was evaporated under reduced pressure, water was added the mixture was extracted with ethyl acetate (×3) the organic layer was washed with 1 N hydrochloric acid The organic layer was dried with anhydrous sodium sulfate the solvent was evaporated under reduced pressure a solution of the resulting residue in ethyl acetate (40 mL) was added to 10% palladium-carbon (dry; 222 mg) the mixture was stirred at room temperature for 2 hours the mixture was filtered through celite The solvent was evaporated under reduced pressure