2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 86602416, compound

HRID 2373239Notes

Reaction equation

HRID 2373239 reaction equation
[C:1](/[C:9](=[CH:15]/[C:16]1[CH:17]=[N:18][C:19]([Cl:22])=[CH:20][CH:21]=1)/[C:10]([O:12][CH2:13][CH3:14])=[O:11])(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH2:23][C:24]1[N:28]([CH2:29][CH3:30])[N:27]=[CH:26][CH:25]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C([O-])(O)=O.[Na+]>CN1CCCC1=O>[Cl:22][C:19]1[N:18]=[CH:17][C:16]([C:15]2[C:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])=[C:1]([C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[N:23]=[C:24]3[N:28]([CH2:29][CH3:30])[N:27]=[CH:26][C:25]=23)=[CH:21][CH:20]=1

Participants

6

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 3373101-Ethyl-1H-pyrazol-5-amine2×HCID 516892Sodium BicarbonateHCID 86602399HCID 86602399, compound

Product 1

HCID 86602416HCID 86602416, compoundYield 77.9%

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
140 °C

Procedure

A mixture of ethyl (2Z)-2-benzoyl-3-(6-chloro-3-pyridyl)acrylate (2.018 g) and 5-amino-1-ethylpyrazole (710 mg) in N-methylpyrrolidone (15 ml) was heated at 140° C. for 3.5 hours. Another 5-amino-1-ethylpyrazole (200 mg) was added and the mixture was heated at 140° C. for 2 hours. After cooling, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.45 g) was added and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into saturated aqueous NaHCO3 and extracted with EtOAc. The organic layer was washed with saturated aqueous NaHCO3 (×4), brine, dried over anhydrous MgSO4 and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel eluting with a mixture of EtOAc and n-hexane (1:7) to give ethyl 4-(6-chloro-3-pyridyl)-1-ethyl-6-phenyl-1H-pyrazolo[3,4-b]pyridine-5-carboxylate (2.024 g) as a brown oil.

Workup

  1. temperaturethe mixture was heated at 140° C. for 2 hours
  2. temperatureAfter cooling
  3. extractionextracted with EtOAc
  4. washThe organic layer was washed with saturated aqueous NaHCO3 (×4), brine
  5. dry with materialdried over anhydrous MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash column chromatography on silica gel eluting with a mixture of EtOAc and n-hexane (1:7)

Sources & evidence

ORD record
ord-d70aaa0318be41179bf465703211b383
Source dataset
uspto-grants-2008_12
Patent number
US07459451B2

Reaction notes

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