2-Fluoro-4-methoxyaniline → HCID 13912593, compound

HRID 1788660Notes

Reaction equation

HRID 1788660 reaction equation
Br[C:2]1[CH:19]=[C:18]([F:20])[C:17]([F:21])=[CH:16][C:3]=1[C:4]([C:6](=[CH:12][N:13]([CH3:15])C)[C:7]([O:9][CH2:10][CH3:11])=[O:8])=[O:5].[F:22][C:23]1[CH:29]=[C:28]([O:30][CH3:31])[CH:27]=[CH:26]C=1N>C1C=CC=CC=1>[F:21][C:17]1[CH:16]=[C:3]2[C:2](=[CH:19][C:18]=1[F:20])[N:13]([C:15]1[CH:26]=[CH:27][C:28]([O:30][CH3:31])=[CH:29][C:23]=1[F:22])[CH:12]=[C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[C:4]2=[O:5]

Participants

4

Reactant 2

HCID 37563832-Fluoro-4-methoxyanilineHCID 54315855HCID 54315855, compound

Product 1

HCID 13912593HCID 13912593, compoundYield 52%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Ethyl 2-(2-bromo-4,5-difluorobenzoyl)-3-dimethylaminoacrylate (1.09 g) and 2-fluoro-4-methoxyaniline (0.51 g) are dissolved in benzene (10 ml), and the mixture is allowed to stand at room temperature for 2 hours. The reaction mixture is washed with diluted hydrochloric acid and saturated aqueous sodium chloride, and dried over sodium sulfate. After distilling off the solvent, the residue is dissolved in anhydrous dioxane (20 ml) and thereto is added 60% sodium hydride (0.14 g). The mixture is stirred at room temperature for one hour and further refluxed for one hour. After cooling, the reaction mixture is poured into saturated aqueous ammonium chloride under ice-cooling. The precipitated crystals are separated by filtration, washed with water, purified by silica gel column chromatography (solvent, dichloromethane:methanol=80:1), and then recrystallized from ethanol to give ethyl 6,7-difluoro-1-(2-fluoro-4-methoxyphenyl)-1,4-dihydro-4-oxoquinoline-3-carboxylate (0.59 g) as pale yellow needles, m.p. 170°-171° C.

Workup

  1. washThe reaction mixture is washed with diluted hydrochloric acid and saturated aqueous sodium chloride
  2. dry with materialdried over sodium sulfate
  3. distillationAfter distilling off the solvent
  4. dissolutionthe residue is dissolved in anhydrous dioxane (20 ml)
  5. additionis added 60% sodium hydride (0.14 g)
  6. temperaturefurther refluxed for one hour
  7. temperatureAfter cooling
  8. additionthe reaction mixture is poured into saturated aqueous ammonium chloride under ice-
  9. temperaturecooling
  10. customThe precipitated crystals are separated by filtration
  11. washwashed with water
  12. custompurified by silica gel column chromatography (solvent, dichloromethane:methanol=80:1)
  13. customrecrystallized from ethanol

Sources & evidence

ORD record
ord-266ae5f07b5c46bc8eea2a4cb77396f0
Source dataset
uspto-grants-1987_08
Patent number
US04684648

Reaction notes

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