Ammonium Chloride → ethyl 2,6-dimethyl-7-oxo-6,7-dihydro-1H-pyrrolo[2,3-c]pyridine-3-carboxylate

HRID 1526970Notes

Reaction equation

HRID 1526970 reaction equation
[CH3:1][N:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:14](=O)[CH3:15])[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:4]([N+:17]([O-])=O)[C:3]1=[O:20].[Cl-].[NH4+]>C(O)C.O.[Fe]>[CH3:15][C:14]1[NH:17][C:4]2[C:3](=[O:20])[N:2]([CH3:1])[CH:7]=[CH:6][C:5]=2[C:8]=1[C:9]([O:11][CH2:12][CH3:13])=[O:10]

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 89739130Ethyl 2-(1-methyl-3-nitro-2-oxo-1,2-dihydropyridin-4-yl)-3-oxobutanoate

Product 1

HCID 117778993ethyl 2,6-dimethyl-7-oxo-6,7-dihydro-1H-pyrrolo[2,3-c]pyridine-3-carboxylateYield 75%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

To a solution of ethyl 2-(1-methyl-3-nitro-2-oxo-1,2-dihydropyridin-4-yl)-3-oxobutanoate (2.5 g, 8.8 mmol) in ethanol (50 mL) was added ammonium chloride (0.5 g, 9 mmol) in water (5 mL) at room temperature. The mixture was stirred and heated to reflux. Then iron powder (0.5 g, 8.9 mmol) was added in one portion. The mixture was stirred at reflux for 2 hours. Once starting material was consumed, the resultant mixture was filtered when it was hot, and the filtrate was concentrated to give a residue. The residue was purified by column chromatography (silica gel, dichloromethane/methanol=10:1) to give ethyl 2,6-dimethyl-7-oxo-6,7-dihydro-1H-pyrrolo[2,3-c]pyridine-3-carboxylate (1.5 g, 75%) as a brown solid. LRMS (M+H+) m/z: calcd 234.1; found 234. 1H NMR (400 MHz, d6-DMSO): δ 12.54 (s, 1H), 7.30 (d, J=5.1 Hz, 1H), 6.78 (d, J=5.1 Hz, 1H), 4.24 (q, J=5.1 Hz, 2H), 3.51 (s, 3H), 2.56 (s, 3H), 1.32 (t, J=5.1 Hz, 3H).

Workup

  1. temperatureheated to reflux
  2. stirringThe mixture was stirred
  3. temperatureat reflux for 2 hours
  4. customOnce starting material was consumed
  5. filtrationthe resultant mixture was filtered when it
  6. concentrationthe filtrate was concentrated
  7. customto give a residue
  8. customThe residue was purified by column chromatography (silica gel, dichloromethane/methanol=10:1)

Sources & evidence

ORD record
ord-1388d0d3c5d04f2bbd6c1edf17cb9ecb
Source dataset
uspto-grants-2015_07
Patent number
US09085583B2

Reaction notes

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