Methyl 3-amino-2-[(tert-butoxycarbonyl)amino]benzoate → 2,3-Diaminobenzoic acid methyl ester

HRID 1398731Notes

Reaction equation

HRID 1398731 reaction equation
[NH2:1][C:2]1[C:3]([NH:12]C(OC(C)(C)C)=O)=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]>FC(F)(F)C(O)=O>[NH2:12][C:3]1[C:2]([NH2:1])=[CH:11][CH:10]=[CH:9][C:4]=1[C:5]([O:7][CH3:8])=[O:6]

Participants

3

Reactant 1

HCID 53407727Methyl 3-amino-2-[(tert-butoxycarbonyl)amino]benzoate

Product 1

HCID 5718252,3-Diaminobenzoic acid methyl esterYield 64%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

Methyl 3-amino-2-[(tert-butoxycarbonyl)amino]benzoate (61.8 g, 232 mmol) was added to trifluoroacetic acid (250 mL), and the mixture was stirred at room temperature for 3 hr. Trifluoroacetic acid was evaporated in vacuo, and the resulting solid was suspended in ethyl acetate (200 mL), collected by filtration and washed with ethyl acetate (50 mL). The solid was partitioned between ethyl acetate (300 mL) and saturated aqueous sodium hydrogen carbonate (400 mL), and the aqueous layer was separated and extracted with ethyl acetate (300 mL). The combined organic layer was washed with water (300 mL×2) and concentrated in vacuo to give the title compound (24.6 g, 148 mmol, 64%) as a brown solid. The filtrate described above was concentrated in vacuo, and the resulting solid was collected by filtration and washed with ethyl acetate. The filtrate was concentrated in vacuo, and the resulting solid was collected by filtration and washed with diethyl ether. The combined solid was partitioned between ethyl acetate (100 mL) and saturated aqueous sodium hydrogen carbonate (100 mL), and the aqueous layer was separated and extracted with ethyl, acetate). The combined organic layer was washed with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give the title compound (8.29 g, 49.9 mmol, 22%) as a brown solid. Total amount: 32.9 g, 198 mmol, 85%.

Workup

  1. customTrifluoroacetic acid was evaporated in vacuo
  2. filtrationcollected by filtration
  3. washwashed with ethyl acetate (50 mL)
  4. customThe solid was partitioned between ethyl acetate (300 mL) and saturated aqueous sodium hydrogen carbonate (400 mL)
  5. customthe aqueous layer was separated
  6. extractionextracted with ethyl acetate (300 mL)
  7. washThe combined organic layer was washed with water (300 mL×2)
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-53a8eb925e0c43e883664aa48504a861
Source dataset
uspto-grants-2014_12
Patent number
US08901141B2

Reaction notes

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