2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 15591001, compound

HRID 255639Notes

Reaction equation

HRID 255639 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][C:13](=[O:19])[CH2:14][C:15]([O:17][CH3:18])=[O:16])[CH:5]=[CH:6][C:7]=1[N:8]([CH3:10])[CH3:9].[F:20][C:21]1[CH:27]=[CH:26][C:24]([NH2:25])=[CH:23][CH:22]=1.Cl[C:29]1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>CN(C)C=O.O1CCOCC1.C1C=CC=CC=1>[F:20][C:21]1[CH:27]=[CH:26][C:24]([N:25]2[C:11]([C:4]3[CH:5]=[CH:6][C:7]([N:8]([CH3:9])[CH3:10])=[C:2]([CH3:1])[CH:3]=3)=[CH:12][C:13](=[O:19])[C:14]([C:15]([O:17][CH3:18])=[O:16])=[CH:29]2)=[CH:23][CH:22]=1

Participants

7

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 97314-FluoroanilineHCID 53667192HCID 53667192, compound

Product 1

HCID 15591001HCID 15591001, compoundYield 61.8%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent

Procedure

In 10 ml of N,N-dimethylformamide was dissolved 2.0 g of methyl 5-(3-methyl-4-dimethylaminophenyl)-3-oxo-4-pentenoate, and 1.1 g of N,N-dimethylformamidodimethylacetal was added to the resulting solution, after which they were reacted at 70° C. for 1.5 hours. To the reaction mixture was then added 1.0 g of p-fluoroaniline at 70° C., and they were reacted at 80° C. for 2 hours and further at 140° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the solvent was removed by distillation under reduced pressure. The residue was purified by a column chromatography (Wako Silica Gel C-200; eluent: chloroform) to obtain an oily substance. This oily substance was dissolved in 30 ml of dioxane, and to this solution was added dropwise a solution of 2.1 g of 2,3-dichloro-5,6-dicyano-p-benzoquinone in 10 ml of benzene at 80° C. Thereafter, the mixture was subjected to reaction at the same temperature for 30 minutes and the solvent was removed by distillation under reduced pressure. The residue was suspended in 50 ml of chloroform and 50 ml of water, and after adjusting this suspension to a pH 7.5 with sodium hydrogencarbonate, the organic layer was separated, washed successively with 10 ml of water and 20 ml of a saturated aqueous solution of sodium chloride and then dried with anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure to obtain 1.8 g of methyl 1-(4-fluorophenyl)-6-(3-methyl-4-dimethylaminophenyl)-4-oxo-1,4-dihydronicotinate having a melting point of 217°-220° C.

Workup

  1. additionwas added to the resulting solution
  2. customafter which they were reacted at 70° C. for 1.5 hours
  3. customthey were reacted at 80° C. for 2 hours and further at 140° C. for 3 hours
  4. customAfter completion of the reaction
  5. customthe solvent was removed by distillation under reduced pressure
  6. customThe residue was purified by a column chromatography (Wako Silica Gel C-200; eluent: chloroform)
  7. customto obtain an oily substance
  8. customThereafter, the mixture was subjected to reaction at the same temperature for 30 minutes
  9. customthe solvent was removed by distillation under reduced pressure
  10. customthe organic layer was separated
  11. washwashed successively with 10 ml of water and 20 ml of a saturated aqueous solution of sodium chloride
  12. dry with materialdried with anhydrous magnesium sulfate
  13. customThe solvent was removed by distillation under reduced pressure

Sources & evidence

ORD record
ord-397bf72732be4f7da309bf26bda9d894
Source dataset
uspto-grants-1987_10
Patent number
US04698352

Reaction notes

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