4-Imidazol-1-yl-2-methyl-6-nitro-phenylamine → 5-Imidazol-1-yl-3-methyl-benzene-1,2-diamine

HRID 970342Notes

Reaction equation

HRID 970342 reaction equation
[N:1]1([C:6]2[CH:11]=[C:10]([N+:12]([O-])=O)[C:9]([NH2:15])=[C:8]([CH3:16])[CH:7]=2)[CH:5]=[CH:4][N:3]=[CH:2]1>[Pd].O>[N:1]1([C:6]2[CH:11]=[C:10]([NH2:12])[C:9]([NH2:15])=[C:8]([CH3:16])[CH:7]=2)[CH:5]=[CH:4][N:3]=[CH:2]1

Participants

4

Reactant 1

HCID 220210264-Imidazol-1-yl-2-methyl-6-nitro-phenylamine

Product 1

HCID 104199825-Imidazol-1-yl-3-methyl-benzene-1,2-diamineYield 91%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent

Procedure

To 4-imidazol-1-yl-2-methyl-6-nitro-phenylamine (350 mg, 1.61 mmol) and 10% Palladium on carbon (40 mg) were added degassed methanol (5 mL) and TFA (5 drops). The reaction mixture was flushed and evacuated with hydrogen/vacuum line, stirred at room temperature for 14 h under hydrogen atmosphere (hydrogen balloon). The dark reaction mixture was filtered through a pad of celite and rinsed with methanol. Concentration of the filtrate gave the residue, which was diluted with water, and extracted with ethyl acetate. The combined organic layers were washed with saturated NaHCO3, and brine and dried over Na2SO4. Concentration to dryness gave the title compound (275 mg, 91%) as a solid. 1H NMR (300 MHz, CD3OD) δ 7.87 (1H, s), 7.34 (1H, s), 7.05 (1H, s), 6.72 (1H, d, J=2.4 Hz), 6.65 (1H, d, J=2.4 Hz) 2.21 (3H, s). LCMS (M+H)+ m/z 189 (t=0.23 min.). Procedure for the Preparation of 3,4-diamino-5-methyl-benzonitrile

Workup

  1. customdegassed methanol (5 mL) and TFA (5 drops)
  2. customThe reaction mixture was flushed
  3. customevacuated with hydrogen/vacuum line
  4. customThe dark reaction mixture
  5. filtrationwas filtered through a pad of celite
  6. washrinsed with methanol
  7. customConcentration of the filtrate gave the residue, which
  8. extractionextracted with ethyl acetate
  9. washThe combined organic layers were washed with saturated NaHCO3, and brine
  10. dry with materialdried over Na2SO4
  11. concentrationConcentration to dryness

Sources & evidence

ORD record
ord-12ff0bfce9d84b5a93e5f3e6fa169d2e
Source dataset
uspto-grants-2007_12
Patent number
US07312215B2

Reaction notes

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