Nitric Acid → 4-methyl-3-[4-(5-methyl-1-phenyl-1H-pyrazol-4-yl)-imidazol-1-yl]-benzoic acid methyl ester

HRID 491842Notes

Reaction equation

HRID 491842 reaction equation
[N+]([O-])(O)=O.[NH+]([O-])=O.[CH3:8][O:9][C:10](=[O:36])[C:11]1[CH:16]=[CH:15][C:14]([CH3:17])=[C:13]([N:18]2[CH:22]=[C:21]([C:23]3[CH:24]=[N:25][N:26]([C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)[C:27]=3[CH3:28])[N:20]=[C:19]2S)[CH:12]=1.C([O-])(O)=O.[Na+]>CC(O)=O>[CH3:8][O:9][C:10](=[O:36])[C:11]1[CH:16]=[CH:15][C:14]([CH3:17])=[C:13]([N:18]2[CH:22]=[C:21]([C:23]3[CH:24]=[N:25][N:26]([C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)[C:27]=3[CH3:28])[N:20]=[CH:19]2)[CH:12]=1

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 516892Sodium BicarbonateHCID 178497764HCID 178497764, compoundHCID 178526385HCID 178526385, compound

Product 1

HCID 588613424-methyl-3-[4-(5-methyl-1-phenyl-1H-pyrazol-4-yl)-imidazol-1-yl]-benzoic acid methyl esterYield 82%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To 1 mL of 20% HNO3 was added 28 mg of HNO2. This mixture was then added to 3-[2-mercapto-4-(5-methyl-1-phenyl-1H-pyrazol-4-yl)-imidazol-1-yl]-4-methyl-benzoic acid methyl ester (280 mg, 0.69 mmol) suspended in 5 mL of rapidly stirring HOAc over 15 min. After stirring an additional 5 min, the solution was poured into ice-cold water. The pH was adjusted to about 7 with NaHCO3, and the mixture was extracted with EtOAc. The extract was washed once with brine, dried with Na2SO4, filtered, and concentrated. The resulting residue was chromatographed (5-60% EtOAc in hexanes) to provide 210 mg (0.56 mmol, 82%) of 4-methyl-3-[4-(5-methyl-1-phenyl-1H-pyrazol-4-yl)-imidazol-1-yl]-benzoic acid methyl ester. ESI MS m/z 373 [C22H20N4O2+H]+.

Workup

  1. additionthe solution was poured into ice-cold water
  2. extractionthe mixture was extracted with EtOAc
  3. washThe extract was washed once with brine
  4. dry with materialdried with Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe resulting residue was chromatographed (5-60% EtOAc in hexanes)

Sources & evidence

ORD record
ord-3c58880043a641809edfa4c8ea9b5dfb
Source dataset
uspto-grants-2009_05
Patent number
US07531560B2

Reaction notes

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