Toluene → Ethyl 2-fluoro-4-(2-nitrophenylamino)benzoate

HRID 1792479Notes

Reaction equation

HRID 1792479 reaction equation
Br[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[C:4]([F:13])[CH:3]=1.[N+:14]([C:17]1[CH:23]=[CH:22][CH:21]=[CH:20][C:18]=1[NH2:19])([O-:16])=[O:15].C(=O)([O-])[O-].[Cs+].[Cs+].C1(C)C=CC=CC=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O>[F:13][C:4]1[CH:3]=[C:2]([NH:19][C:18]2[CH:20]=[CH:21][CH:22]=[CH:23][C:17]=2[N+:14]([O-:16])=[O:15])[CH:12]=[CH:11][C:5]=1[C:6]([O:8][CH2:9][CH3:10])=[O:7]

Participants

8

Reactant 4

HCID 1140TolueneHCID 69462-NitroanilineHCID 10796Cesium carbonateHCID 22031817Ethyl 4-bromo-2-fluorobenzoate

Product 1

HCID 22032336Ethyl 2-fluoro-4-(2-nitrophenylamino)benzoateYield 77.1%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolvent

Procedure

1.0 g ethyl 4-bromo-2-fluorobenzoate, 0.56 g 2-nitroaniline, 1.85 g cesium carbonate, 37 mg tris(dibenzylideneacetone)-dipalladium (0), 38 mg 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemic mixture) and 15 mL toluene were stirred at 100° C. for 24 hours under nitrogen atmosphere. Water was added thereto, then the reaction mixture was extracted with ether, and the organic layer was dried over sodium sulfate. After the solvent was evaporated, the residue was purified by NH silica gel chromatography (ethyl acetate/hexane). By recrystallization from ethyl acetate/hexane, 0.95 g of the title compound was obtained as yellow crystals.

Workup

  1. extractionthe reaction mixture was extracted with ether
  2. dry with materialthe organic layer was dried over sodium sulfate
  3. customAfter the solvent was evaporated
  4. customthe residue was purified by NH silica gel chromatography (ethyl acetate/hexane)
  5. customBy recrystallization from ethyl acetate/hexane

Sources & evidence

ORD record
ord-ceab4b5f989746cf9e16193cc124bb05
Source dataset
uspto-grants-2006_07
Patent number
US07074801B1

Reaction notes

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