Chloranil → HCID 20183850, compound

HRID 255670Notes

Reaction equation

HRID 255670 reaction equation
[CH:1]1([CH:9]=[CH:10][C:11](=[O:17])[CH2:12][C:13]([O:15]C)=[O:14])[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[OH:18][C:19]1[CH:25]=[CH:24][C:22]([NH2:23])=[C:21]([CH3:26])[CH:20]=1.Cl[C:28]1C(=O)C(Cl)=C(Cl)C(=O)C=1Cl>C1C=CC=CC=1.CN(C)C=O.O1CCOCC1>[CH:1]1([C:9]2[N:23]([C:22]3[CH:24]=[CH:25][C:19]([OH:18])=[CH:20][C:21]=3[CH3:26])[CH:28]=[C:12]([C:11](=[O:17])[CH:10]=2)[C:13]([OH:15])=[O:14])[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1

Participants

7

Reactant 3

HCID 8371ChloranilHCID 178194-Amino-m-cresolHCID 57149955HCID 57149955, compound

Product 1

HCID 20183850HCID 20183850, compoundYield 48.4%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent

Procedure

In 5 ml of benzene was dissolved 0.3 g of methyl 5-cyclooctyl-3-oxo-4-pentenoate, and 0.3 g of N,N-dimethylformamidodimethylacetal was added thereto. They were reacted at 70° C. for one hour. Then, the reaction mixture was cooled to room temperature, and 0.27 g of 4-hydroxy-2-methylaniline was added thereto. The resulting mixture was subjected to reaction at room temperature for 2 hours. After completion of this 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: toluene/ethyl acetate (50:1 by volume) mixture). The fraction containing the objective substance was concentrated, and the oily substance thus obtained was dissolved in 5 ml of N,N-dimethylformamide and the resulting mixture was refluxed for 4 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/ethanol (50:1 by volume) mixture). The fraction containing the objective substance was concentrated and the oily substance thus obtained was dissolved in 5 ml of dioxane, and 0.2 g of 2,3,5,6-tetrachloro-p-benzoquinone was added thereto, and they were reacted at 80°-90° C. for 30 minutes. The reaction mixture was cooled to room temperature, and the precipitated crystals were collected by filtration. These crystals were dissolved in 20 ml of chloroform, and after removing the insolubles, the chloroform was removed by distillation under reduced pressure. To the residue was added 5 ml of a 1N aqueous sodium hydroxide solution and 5 ml of methanol, and they were reacted at room temperature for 30 minutes. After the methanol was removed by distillation under reduced pressure, the resulting solution was adjusted to a pH of 6.5 with 2N hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain 0.14 g of 6-cyclooctyl-1-(4-hydroxy-2-methylphenyl)-4-oxo-1,4-dihydronicotinic acid having a melting point of 118°-120° C.

Workup

  1. additionwas added
  2. customThey were reacted at 70° C. for one hour
  3. customThe resulting mixture was subjected to reaction at room temperature for 2 hours
  4. customAfter completion of this 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: toluene/ethyl acetate (50:1 by volume) mixture)
  7. additionThe fraction containing the objective substance
  8. concentrationwas concentrated
  9. customthe oily substance thus obtained
  10. temperaturethe resulting mixture was refluxed for 4 hours
  11. customAfter completion of the reaction
  12. customthe solvent was removed by distillation under reduced pressure
  13. customthe residue was purified by a column chromatography (Wako Silica Gel C-200; eluent: chloroform/ethanol (50:1 by volume) mixture)
  14. additionThe fraction containing the objective substance
  15. concentrationwas concentrated
  16. customthe oily substance thus obtained
  17. customthey were reacted at 80°-90° C. for 30 minutes
  18. temperatureThe reaction mixture was cooled to room temperature
  19. filtrationthe precipitated crystals were collected by filtration
  20. dissolutionThese crystals were dissolved in 20 ml of chloroform
  21. customafter removing the insolubles
  22. customthe chloroform was removed by distillation under reduced pressure
  23. additionTo the residue was added 5 ml of a 1N aqueous sodium hydroxide solution and 5 ml of methanol, and they
  24. customwere reacted at room temperature for 30 minutes
  25. customAfter the methanol was removed by distillation under reduced pressure
  26. filtrationthe precipitated crystals were collected by filtration
  27. washwashed with water
  28. customdried

Sources & evidence

ORD record
ord-3f2bc03b5205443fa62df846f3eb35d9
Source dataset
uspto-grants-1987_10
Patent number
US04698352

Reaction notes

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