2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 66693755, compound

HRID 472820Notes

Reaction equation

HRID 472820 reaction equation
[CH3:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][CH:3]=1.[NH:10]1[C:14]([NH2:15])=[CH:13][CH:12]=[N:11]1.O=[C:17]([CH3:23])[CH2:18][C:19]([O:21][CH3:22])=[O:20].C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C1COCC1.CCCCCCC.N1CCCCC1>[CH3:23][C:17]1[C:18]([C:19]([O:21][CH3:22])=[O:20])=[C:6]([C:5]2[CH:8]=[CH:9][C:2]([CH3:1])=[CH:3][CH:4]=2)[N:10]2[N:11]=[CH:12][CH:13]=[C:14]2[N:15]=1

Participants

8

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 77254-MethylbenzaldehydeHCID 7757Methyl acetoacetateHCID 74561Pyrazol-3-ylamine

Product 1

HCID 66693755HCID 66693755, compoundYield 66.2%

Reagents, catalysts & solvents 3

HCID 8082PiperidineCatalystHCID 8028TetrahydrofuranSolventHCID 8900HeptaneSolvent

Procedure

To a stirred solution of 4-methylbenzaldehyde (723 mg, 6.02 mmol), 1H-pyrazol-5-amine (500 mg, 6.02 mmol), and methyl 3-oxobutanoate (769 mg, 6.62 mmol) in THF (80 mL) and heptane (20 mL) was added piperidine (10 mL, 0.101 mmol). The reaction mixture was heated at reflux for 20 h. The solvent was evaporated and the crude material was dissolved in CH2Cl2. DDQ (1229 mg, 5.42 mmol) was added and the mixture was stirred at room temperature for 1 h. The solvent was evaporated. Purification by silica gel chromatography provided the title compound (1120 mg, 66.2%). 1H-NMR (500 MHz, CD Cl3) δ ppm 2.44 (3H, s), 2.65 (3H, s), 3.63 (3H, s), 6.65 (1H, d, J=2.4 Hz), 7.34 (2H, d, J=8.1 Hz), 7.52 (2H, d, J=8.1 Hz), 8.10 (1H, d, J=2.4 Hz).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 20 h
  3. customThe solvent was evaporated
  4. dissolutionthe crude material was dissolved in CH2Cl2
  5. customThe solvent was evaporated
  6. customPurification by silica gel chromatography

Sources & evidence

ORD record
ord-a48a7fe3618c43dbbf16daa2c891a49d
Source dataset
uspto-grants-2014_01
Patent number
US08633200B2

Reaction notes

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