2-Chloro-4-nitrobenzoic acid → 2-(4-Fluoroanilino)-4-nitrobenzoic acid

HRID 2191623Notes

Reaction equation

HRID 2191623 reaction equation
Cl[C:2]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[F:14][C:15]1[CH:21]=[CH:20][C:18]([NH2:19])=[CH:17][CH:16]=1.CN1CCOCC1>[Cu].[Cu]Cl.CN(C)C(=O)C>[F:14][C:15]1[CH:21]=[CH:20][C:18]([NH:19][C:2]2[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:3]=2[C:4]([OH:6])=[O:5])=[CH:17][CH:16]=1

Participants

7

Reactant 3

HCID 74482-Chloro-4-nitrobenzoic acidHCID 79724-MethylmorpholineHCID 97314-Fluoroaniline

Product 1

HCID 576678972-(4-Fluoroanilino)-4-nitrobenzoic acid

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 62652Cuprous chlorideCatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
115 °C

Procedure

To N,N-dimethylacetamide 150 mL solution of 2-chloro-4-nitrobenzoic acid 30 g, were added 4-fluoroaniline 29 mL, copper powder 2.8 g, copper (I) chloride 5.3 g and N-methylmorpholine 33 mL at room temperature, and it was stirred at 110 to 120° C. for 10 hours. After the reaction mixture was cooled to room temperature, insoluble matter was filtrated, and 1.0 mol/L hydrochloric acid 700 mL and ethyl acetate 700 mL were added to it. The organic layer was separated and collected,dried over anhydrous magnesium sulfate after sequential washing with 1.0 mol/L hydrochloric acid and saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. Diisopropyl ether was added to the obtained residue, solid matter was filtrated to give 2-(4-fluoroanilino)-4-nitrobenzoic acid 9.7 g of red solid.

Workup

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. filtrationinsoluble matter was filtrated
  3. addition1.0 mol/L hydrochloric acid 700 mL and ethyl acetate 700 mL were added to it
  4. customThe organic layer was separated
  5. washafter sequential washing with 1.0 mol/L hydrochloric acid and saturated sodium chloride aqueous solution
  6. customthe solvent was removed under reduced pressure
  7. additionDiisopropyl ether was added to the obtained residue, solid matter
  8. filtrationwas filtrated

Sources & evidence

ORD record
ord-82837cfea5b54468afe5ee4d1600157a
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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