Aniline → Methyl 3-(phenylamino)benzoate

HRID 2422267

Reaction equation

HRID 2422267 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[NH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(=O)([O-])[O-].[Cs+].[Cs+].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:12]([C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

6

Reactant 4

HCID 6115AnilineHCID 10796Cesium carbonateHCID 12070Methyl 3-bromobenzoateHCID 634876Binap, (A+-)-

Product 1

HCID 614856Methyl 3-(phenylamino)benzoateYield 34.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of methyl 3-bromobenzoate (5.87 g, 27.3 mmol), aniline (3.73 mL, 41.0 mmol), cesium carbonate (12.5 g, 38.2 mmol), tris(dibenzylidenacetone)dipalladium (0) (1.0 g, 1.09 mmol), rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (1.02 g, 1.64 mmol) and toluene (60 mL) was stirred under a nitrogen atmosphere at 80° C. for 16 hrs. The reaction mixture was cooled, washed with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=10/1-4/1) to give the title compound (2.13 g, yield 34%) as pale-yellow crystalsitle compound.

Workup

  1. temperatureThe reaction mixture was cooled
  2. washwashed with water and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=10/1-4/1)

Sources & evidence

ORD record
ord-322484b5bc5e4d83a72afe64281b1bcf
Source dataset
uspto-grants-2011_06
Patent number
US07960369B2

Linked notes

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