Methyl 6-amino-5-nitropyridine-2-carboxylate → Methyl 5,6-diamino-2-pyridinecarboxylate

HRID 39659Notes

Reaction equation

HRID 39659 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-])=O)=[C:7]([NH2:14])[N:6]=1)=[O:4]>CO>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([NH2:11])=[C:7]([NH2:14])[N:6]=1)=[O:4]

Participants

3

Reactant 1

HCID 12097746Methyl 6-amino-5-nitropyridine-2-carboxylate

Product 1

HCID 12097747Methyl 5,6-diamino-2-pyridinecarboxylateYield 79.8%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Methyl ester 3 (3.5 g, 18.0 mmol) was dissolved in methanol (300 mL) and EtOAc (300 mL) and the solution was degassed with Ar. After the addition of Pd/C (10 wt %, 0.7 g) the reaction mixture was stirred for 4 h under a hydrogen atmosphere. Filtration through a pad of Celite with EtOAc, evaporation of the solvent and purification by flash chromatography (EtOAc/MeOH 15:1) yielded 2.4 g (79%) of 4 as a deep red powder. Data of 4: Rf 0.42 (EtOAc/MeOH 15:1). 1H NMR (300 MHz, DMSO-d6): δ 3.68 (s, 3H), 5.51 (brs, 2H), 5.78 (brs, 2H), 6.67 (d, J1) 7.7 Hz, 1H), 7.21 (d, J1) 7.7 Hz, 1H). 13C NMR (75 MHz, DMSO-d6): δ 51.88, 116.32, 117.98, 132.40, 135.09, 147.93, 166.30. MS (ESI): m/z (rel intensity) 168 (100).

Workup

  1. customEtOAc (300 mL) and the solution was degassed with Ar
  2. additionAfter the addition of Pd/C (10 wt %, 0.7 g) the reaction mixture
  3. filtrationFiltration through a pad of Celite
  4. customwith EtOAc, evaporation of the solvent and purification by flash chromatography (EtOAc/MeOH 15:1)

Sources & evidence

ORD record
ord-6fff2e72602b4675af9aed4f87b32761
Source dataset
uspto-grants-2013_09
Patent number
US08524899B2

Reaction notes

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