Methyl 2-((tert-butoxycarbonyl)amino)-3-nitrobenzoate → Methyl 3-amino-2-[(tert-butoxycarbonyl)amino]benzoate

HRID 1398730Notes

Reaction equation

HRID 1398730 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[C:18]([N+:19]([O-])=O)=[CH:17][CH:16]=[CH:15][C:10]=1[C:11]([O:13][CH3:14])=[O:12])=[O:7])([CH3:4])([CH3:3])[CH3:2]>CO.[Pd]>[NH2:19][C:18]1[C:9]([NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])=[C:10]([CH:15]=[CH:16][CH:17]=1)[C:11]([O:13][CH3:14])=[O:12]

Participants

4

Reactant 1

HCID 9965968Methyl 2-((tert-butoxycarbonyl)amino)-3-nitrobenzoate

Product 1

HCID 53407727Methyl 3-amino-2-[(tert-butoxycarbonyl)amino]benzoateYield 45,402.301%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

To a suspension of methyl 2-[(tert-butoxycarbonyl)amino]-3-nitrobenzoate (103 g, 0.348 mmol) in methanol (800 mL) was added 10% palladium on carbon (50% wet; 10 g), and the mixture was purged with hydrogen and stirred under balloon pressure hydrogen at room temperature for 5 hr. The catalyst was removed by filtration, and the filtrate was concentrated in vacuo. The residual solid was suspended in diisopropyl ether (300 mL), and the suspension was stirred at room temperature for 3 hr. The resulting solid was collected by filtration and washed with diisopropyl ether to give the title compound (42.0 g, 158 mmol, 45%). The mixture of the removed catalyst described above and a colorless solid (the title compound) was suspended in tetrahydrofuran (200 mL), and the suspension was stirred at room temperature for 30 minutes. The insoluble material (the catalyst) was removed by filtration, and the filtrate was concentrated in vacuo. The residual solid was suspended in diisopropyl ether (300 mL), and the suspension was refluxed for 30 min. The resulting solid was collected by filtration and washed with diisopropyl ether to give the title compound (33.9 g, 127 mmol, 36%) as a colorless solid. Total amount: 75.9 g, 285 mmol, 82%.

Workup

  1. customthe mixture was purged with hydrogen
  2. customThe catalyst was removed by filtration
  3. concentrationthe filtrate was concentrated in vacuo
  4. stirringthe suspension was stirred at room temperature for 3 hr
  5. filtrationThe resulting solid was collected by filtration
  6. washwashed with diisopropyl ether

Sources & evidence

ORD record
ord-687560bcc6514cc9ad7cc20773af694e
Source dataset
uspto-grants-2014_12
Patent number
US08901141B2

Reaction notes

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