Hydrogen Peroxide → HCID 68977144, compound

HRID 969594Notes

Reaction equation

HRID 969594 reaction equation
[NH2:1][C:2]1[N:6]([C:7]([CH3:10])([CH3:9])[CH3:8])[N:5]=[C:4]([C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=2)[C:3]=1[C:20]#[N:21].[OH:22]O.[OH-].[Na+]>O1CCCC1.S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC>[NH2:1][C:2]1[N:6]([C:7]([CH3:9])([CH3:10])[CH3:8])[N:5]=[C:4]([C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=2)[C:3]=1[C:20]([NH2:21])=[O:22]

Participants

6

Reactant 3

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 10589184HCID 10589184, compound

Product 1

HCID 68977144HCID 68977144, compound

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 5-amino-1-tert-butyl-3-(4-nitro-phenyl)-1H-pyrazole-4-carbonitrile (2.85 g, 10 mmol) in 40 mL of tetrahydrofuran were added a 30% aqueous solution of hydrogen peroxide (80 mL), a 1 M solution of sodium hydroxide (20 mL) and 3 g of tetrabutylammonium hydrogensulfate. The reaction mixture was stirred for 48 hours at room temperature and extracted with ethyl acetate (2×200 mL). The organic layers were combined, washed with brine, dried over solid MgSO4, filtered and evaporated. The yellow residue was purified by normal phase silica column chromatography (100% ethyl acetate) to give 750 mg of pure 5-amino-1-tert-butyl-3-(4-nitro-phenyl)-1H-pyrazole-4-carboxylic acid amide. 1H-NMR (DMSO-d6): ppm 1.54 (s, 9H), 6.11 (br s, 2H), 7.81 (d, 2H, J=7.6 Hz), 8.22 (d, 2H, J=7.6 Hz). LC MS (m/e)=304.2 (MH+).

Workup

  1. extractionextracted with ethyl acetate (2×200 mL)
  2. washwashed with brine
  3. dry with materialdried over solid MgSO4
  4. filtrationfiltered
  5. customevaporated
  6. customThe yellow residue was purified by normal phase silica column chromatography (100% ethyl acetate)

Sources & evidence

ORD record
ord-9dbf056fea72460b8a4b7fb48142b4c8
Source dataset
uspto-grants-2007_12
Patent number
US07307097B2

Reaction notes

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