2-Amino-5-(4-methylimidazol-1-yl)benzonitrile → 4-(4-methyl-1H-imidazol-1-yl)-2-aminomethylaniline

HRID 472154

Reaction equation

HRID 472154 reaction equation
[CH3:1][C:2]1[N:3]=[CH:4][N:5]([C:7]2[CH:13]=[CH:12][C:10]([NH2:11])=[C:9]([C:14]#[N:15])[CH:8]=2)[CH:6]=1.[H][H]>N.CO.[Ni+2]>[CH3:1][C:2]1[N:3]=[CH:4][N:5]([C:7]2[CH:13]=[CH:12][C:10]([NH2:11])=[C:9]([CH2:14][NH2:15])[CH:8]=2)[CH:6]=1

Participants

5

Reactant 2

HCID 197097592-Amino-5-(4-methylimidazol-1-yl)benzonitrileHCID 178418361HCID 178418361, compound

Product 1

HCID 582704594-(4-methyl-1H-imidazol-1-yl)-2-aminomethylanilineYield 82%

Reagents, catalysts & solvents 2

HCID 934Nickel cationCatalystHCID 21705897Ammonia methanolSolvent

Procedure

To 4-(4-methyl-1H-imidazol-1-yl)-2-cyanoaniline (15.5 g; 78.2 mmol) dissolved in 10% NH3/methanol was added Raney-Nichel (5 g), the resulting mixture was hydrogenated at 60° C., at an hydrogen pressure of 60 bar, for 24 hours. The nitrogen purged reaction mixture was filtered on celite, the cake was washed with methanol and the combined filtrate and washings evaporated. The residue was purified by column chromatography over silica gel (DCM/MeOH/2M NH3, 85:10:5) evaporation of the combined appropriate fractions afforded the pure titled product as yellow-orange solid (12.9 g, 82%). C11H14N4, MW: 202.26; 1H-NMR (300 MHz, d6-DMSO) ppm: 2.13 (s, 3H), 5.24 (s, 2H), 6.67 (d, 1H), 7.08 (dd, 1H), 7.17 (t, 1H), 7.23 (d, 1H), 7.81 (d, 1H).

Workup

  1. customThe nitrogen purged
  2. customreaction mixture
  3. filtrationwas filtered on celite
  4. washthe cake was washed with methanol
  5. customthe combined filtrate and washings evaporated
  6. customThe residue was purified by column chromatography over silica gel (DCM/MeOH/2M NH3, 85:10:5) evaporation of the combined appropriate fractions

Sources & evidence

ORD record
ord-36d3c6d611b8452b9e71b29f7cdebd38
Source dataset
uspto-grants-2014_01
Patent number
US08633208B2

Linked notes

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