4-Fluoroiodobenzene → Methyl 2-(4-fluoroanilino)-4-((phenylthio)methyl)benzoate

HRID 2191689Notes

Reaction equation

HRID 2191689 reaction equation
Cl.[NH2:2][C:3]1[CH:12]=[C:11]([CH2:13][S:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:10]=[CH:9][C:4]=1[C:5]([O:7][CH3:8])=[O:6].C(=O)([O-])[O-].[Cs+].[Cs+].[F:27][C:28]1[CH:33]=[CH:32][C:31](I)=[CH:30][CH:29]=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>[F:27][C:28]1[CH:33]=[CH:32][C:31]([NH:2][C:3]2[CH:12]=[C:11]([CH2:13][S:14][C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH:10]=[CH:9][C:4]=2[C:5]([O:7][CH3:8])=[O:6])=[CH:30][CH:29]=1

Participants

7

Reactant 3

HCID 96054-FluoroiodobenzeneHCID 10796Cesium carbonateHCID 67343711HCID 67343711, compound

Product 1

HCID 57667962Methyl 2-(4-fluoroanilino)-4-((phenylthio)methyl)benzoate

Reagents, catalysts & solvents 3

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

Procedure

To toluene 9.5 mL suspension of methyl 2-amino-4-((phenylthio)methyl)benzoate hydrochloride 0.96 g, rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl 19 mg, palladium acetate 7 mg and cesium carbonate 3.0 g was added 1-fluoro-4-iodobenzene 1.1 mL, and it was heated and refluxed under nitrogen atmosphere for 3 hours. After the reaction mixture was cooled to room temperature, palladium acetate 7.0 mg was added to it, and it was heated and refluxed for 14 hours. After 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=20:1] to give methyl 2-(4-fluoroanilino)-4-((phenylthio)methyl)benzoate 0.48 g of pale yellow oil.

Workup

  1. temperaturewas heated
  2. temperaturerefluxed under nitrogen atmosphere for 3 hours
  3. temperaturewas heated
  4. temperaturerefluxed for 14 hours
  5. temperatureAfter the 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-9416e5ff54044d48b89c4f35b6ad1b34
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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