Nitric Acid → HCID 19792193, compound

HRID 452186Notes

Reaction equation

HRID 452186 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[C:12]([O:17]C(=O)CCC)(=O)[CH2:13][CH2:14][CH3:15].[N+:23]([O-])([OH:25])=[O:24].[OH-].[Na+]>O>[C:12]([NH:1][C:2]1[C:11]([N+:23]([O-:25])=[O:24])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])(=[O:17])[CH2:13][CH2:14][CH3:15]

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 7798Butyric anhydrideHCID 8635Methyl AnthranilateHCID 14798Sodium Hydroxide

Product 1

HCID 19792193HCID 19792193, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

[step 1] To methyl 2-aminobenzoate (1.5 g, 9.92 mmol) was added butyric anhydride (4.9 mL, 29.76 mmol), and the mixture was stirred at room temperature for 2 hr. Under ice-cooling, fuming nitric acid (1.6 mL) was added dropwise to the mixture, and the mixture was stirred at 0° C. for 20 min. The mixture was adjusted to pH 7 with water and 4 mol/L aqueous sodium hydroxide solution, and extracted with ethyl acetate (150 mL). The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0 to 60/40) to give methyl 2-butyramido-3-nitrobenzoate (1.26 g, 48%). [step 2] Methyl 2-butyramido-3-nitrobenzoate (1.65 g, 6.2 mmol) obtained in step 1 was dissolved in methanol (34 mL), and the mixture was stirred in the presence of 10% palladium carbon (413 mg) under a hydrogen atmosphere at room temperature for 6 hr. The mixture was filtered, and the filtrate was concentrated under reduced pressure to give methyl 3-amino-2-butyramidobenzoate (1.46 g, 100%). [step 3] To methyl 3-amino-2-butyramidobenzoate (1.46 g, 6.2 mmol) obtained in step 2 was added acetic acid (9.0 mL), and the mixture was stirred at 80° C. for 1.5 hr. The mixture was concentrated under reduced pressure, saturated aqueous sodium hydrogen carbonate solution (300 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=80/20 to 50/50) to give the title compound (1.18 g, 87%).

Workup

  1. temperatureUnder ice-cooling
  2. stirringthe mixture was stirred at 0° C. for 20 min
  3. extractionextracted with ethyl acetate (150 mL)
  4. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0 to 60/40)

Sources & evidence

ORD record
ord-098e7ca3714e4e9b8eb22c73e646c39e
Source dataset
uspto-grants-2013_07
Patent number
US08486980B2

Reaction notes

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