Chloranil → Methyl 1-(4-hydroxyphenyl)-6-(2-naphthyl)-4-oxo-1,4-dihydronicotinate

HRID 255637Notes

Reaction equation

HRID 255637 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][CH:9]=[C:10]([C:15](=[O:28])[CH:16]=[CH:17][C:18]2[CH:27]=[CH:26][C:25]3[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=3)[CH:19]=2)[C:11]([O:13][CH3:14])=[O:12])=[CH:4][CH:3]=1.ClC1C(=O)C(Cl)=C(Cl)C(=O)C=1Cl>CN(C)C=O.O1CCOCC1>[OH:1][C:2]1[CH:3]=[CH:4][C:5]([N:8]2[C:17]([C:18]3[CH:27]=[CH:26][C:25]4[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=4)[CH:19]=3)=[CH:16][C:15](=[O:28])[C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9]2)=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 8371ChloranilHCID 178500767HCID 178500767, compound

Product 1

HCID 15590992Methyl 1-(4-hydroxyphenyl)-6-(2-naphthyl)-4-oxo-1,4-dihydronicotinateYield 44.4%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

In 12 ml of N,N-dimethylformamide was dissolved 1.7 g of methyl 2-(4-hydroxyphenylaminomethylene)-5-(2-naphthyl)-3-oxo-4-pentenoate, and they were reacted at 140° C. for 2 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the residue was purified by a column chromatography (Wako Silica Gel C-200; eluent: chloroform/methanol (19:1 by volume) mixture). The purified oily substance was dissolved in 15 ml of dioxane and the resulting solution was heated to 80° C. To this solution was added dropwise at 80° C. a solution formed by dissolving 1.1 g of 2,3,5,6-tetrachloro-p-benzoquinone in 15 ml of dioxane. After this addition was completed, the solvent was removed by distillation under reduced pressure, and to the residue was added 20 ml of a chloroform/methanol (5:1 by volume) mixed solvent. The crystals thus formed were collected by filtration, washed with 5 ml of the same mixed solvent as mentioned above, and then dried to obtain 0.75 g of methyl 1-(4-hydroxyphenyl)-6-(2-naphthyl)-4-oxo-1,4-dihydronicotinate having a melting point of 280° C. or more.

Workup

  1. customwere reacted at 140° C. for 2 hours
  2. customAfter completion of the reaction
  3. customthe solvent was removed by distillation under reduced pressure
  4. customthe residue was purified by a column chromatography (Wako Silica Gel C-200; eluent: chloroform/methanol (19:1 by volume) mixture)
  5. dissolutionThe purified oily substance was dissolved in 15 ml of dioxane
  6. additionTo this solution was added dropwise at 80° C. a solution
  7. customformed
  8. additionAfter this addition
  9. customthe solvent was removed by distillation under reduced pressure
  10. additionto the residue was added 20 ml of a chloroform/methanol (5:1 by volume)
  11. additionmixed solvent
  12. customThe crystals thus formed
  13. filtrationwere collected by filtration
  14. washwashed with 5 ml of the same mixed solvent
  15. customthen dried

Sources & evidence

ORD record
ord-53b066261acc4f0aa776a263e0bb2673
Source dataset
uspto-grants-1987_10
Patent number
US04698352

Reaction notes

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