Ammonium formate → 4-(4-Methyl-1h-imidazol-1-yl)benzenamine

HRID 2366892Notes

Reaction equation

HRID 2366892 reaction equation
C([O-])=O.[NH4+].[CH3:5][C:6]1[N:7]=[CH:8][N:9]([C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-])=O)=[CH:13][CH:12]=2)[CH:10]=1>C(O)C.[Pd]>[CH3:5][C:6]1[N:7]=[CH:8][N:9]([C:11]2[CH:16]=[CH:15][C:14]([NH2:17])=[CH:13][CH:12]=2)[CH:10]=1

Participants

5

Reactant 2

HCID 2723923Ammonium formate2×HCID 160051694-Methyl-1-(4-nitrophenyl)-1H-imidazole

Product 1

HCID 160051704-(4-Methyl-1h-imidazol-1-yl)benzenamineYield 90.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

Ammonium formate (2.202 g, 34.9 mmol) and palladium (10% w/w on carbon, 50% wet, 0.473 g, 4.44 mmol) were added to a solution 4-methyl-1-(4-nitrophenyl)-1H-imidazole (4.73 g, 23.28 mmol) in ethanol (150 mL) and the resulting mixture was refluxed under nitrogen for 1 h then cooled to room temperature. An extra portion of ammonium formate (2.202 g, 34.9 mmol) was then added and the resulting mixture was refluxed for a further hour then cooled to room temperature and filtered through celite. Most of the solvent was removed in vacuo and the residue was loaded on a 50 g SCX column which was eluted with MeOH (5 CV) then with 2N NH3 in MeOH (5 CV). The ammonia fractions were combined and concentrated in vacuo to give 4-(4-methyl-1H-imidazol-1-yl)aniline (3.92 g, 21.06 mmol, 90%) as a yellow solid.

Workup

  1. temperaturethe resulting mixture was refluxed under nitrogen for 1 h
  2. temperaturethe resulting mixture was refluxed for a further hour
  3. temperaturethen cooled to room temperature
  4. filtrationfiltered through celite
  5. customMost of the solvent was removed in vacuo
  6. washwas eluted with MeOH (5 CV)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-132032d583f441b4ae41e7687144151f
Source dataset
uspto-grants-2014_04
Patent number
US08697725B2

Reaction notes

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