Aniline → Methyl 4-anilino-2-(4-fluoroanilino)benzoate

HRID 2191682Notes

Reaction equation

HRID 2191682 reaction equation
[F:1][C:2]1[CH:19]=[CH:18][C:5]([NH:6][C:7]2[CH:16]=[C:15](I)[CH:14]=[CH:13][C:8]=2[C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[NH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.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.C1(C)C=CC=CC=1>[NH:26]([C:15]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[C:7]([NH:6][C:5]2[CH:18]=[CH:19][C:2]([F:1])=[CH:3][CH:4]=2)[CH:16]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

7

Reactant 3

HCID 6115AnilineHCID 10796Cesium carbonateHCID 57667861Methyl 2-(4-fluoroanilino)-4-iodobenzoate

Product 1

HCID 57667985Methyl 4-anilino-2-(4-fluoroanilino)benzoate

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalyst2×HCID 634876Binap, (A+-)-Catalyst2×HCID 1140TolueneSolvent

Procedure

To toluene 2.0 mL suspension of methyl 2-(4-fluoroanilino)-4-iodobenzoate 0.20 g, rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl 10 mg, palladium acetate 4 mg and cesium carbonate 0.35 g was added aniline 0.074 mL, and it was heated and refluxed under nitrogen atmosphere for 3 hours. The reaction mixture was cooled to room temperature, rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl 10 mg and palladium acetate 4 mg were added to it, and it was heated and refluxed under nitrogen atmosphere for 3 hours. The reaction mixture was cooled to room temperature, insoluble matter was filtrated, and the solvent was removed under reduced pressure. The obtained residue was refined by silica gel column chromatography [Fuji SILYSIA Chemical Ltd., PSQ100B(spherical type), eluent; hexane:ethyl acetate=10:1] to give methyl 4-anilino-2-(4-fluoroanilino)benzoate 0.13 g of pale yellow solid.

Workup

  1. temperaturewas heated
  2. temperaturerefluxed under nitrogen atmosphere for 3 hours
  3. temperaturewas heated
  4. temperaturerefluxed under nitrogen atmosphere for 3 hours
  5. temperatureThe reaction mixture was cooled to room temperature
  6. filtrationinsoluble matter was filtrated
  7. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-8191844bb61c4c33bb175a0b2d2a2cd9
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

Loading…