Cesium carbonate → 2-{4-[2-(3,4-Dichloro-phenyl)-ethyl]phenylamino}-5-nitrobenzoic acid methyl ester

HRID 488484Notes

Reaction equation

HRID 488484 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([NH2:17])=[CH:13][CH:12]=2)[CH:5]=[CH:6][C:7]=1[Cl:8].[CH3:18][O:19][C:20](=[O:31])[C:21]1[CH:26]=[C:25]([N+:27]([O-:29])=[O:28])[CH:24]=[CH:23][C:22]=1Br.C(=O)([O-])[O-].[Cs+].[Cs+].C1(C)C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2)C2C=CC(C)=CC=2)=CC=1>C1(C)C=CC=CC=1.CCOCC.[Pd]>[CH3:18][O:19][C:20](=[O:31])[C:21]1[CH:26]=[C:25]([N+:27]([O-:29])=[O:28])[CH:24]=[CH:23][C:22]=1[NH:17][C:14]1[CH:13]=[CH:12][C:11]([CH2:10][CH2:9][C:4]2[CH:5]=[CH:6][C:7]([Cl:8])=[C:2]([Cl:1])[CH:3]=2)=[CH:16][CH:15]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 245494Methyl 2-Bromo-5-nitrobenzoateHCID 112541254-(3,4-Dichlorophenethyl)anilineHCID 18398271Di-p-tolylphosphino-1,1'-binaphthyl

Product 1

HCID 537377402-{4-[2-(3,4-Dichloro-phenyl)-ethyl]phenylamino}-5-nitrobenzoic acid methyl esterYield 64.4%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

A mixture of 4-[2-(3,4-dichlorophenyl)-ethyl]benzenamine (600 mg, 2.25 mmol), 2-bromo-5-nitrobenzoic acid methyl ester (489 mg, 1.88 mmol), cesium carbonate (857 mg, 2.62 mmol), tris(dibenzylideneacetone-dipaladium(0) (51 mg, 0.056 mmol) and (S)-(2,2′-bis(di-p-tolylphosphino-1,1′-binaphthyl (98%, (S)-tol-BINAP) (58 mg, 0.085 mmol) (Ligand/Pd=1.5) in anhydrous toluene (16 mL) was heated to 100° C. for 12 hours under N2. After cooling, the reaction mixture was diluted with ether, filtered through celite and rinsed thoroughly with ether. The filtrate was evaporated to dryness to give a brown residue. Purification by flash chromatography (silica gel, 5% EtOAc/hexane) yielded 540 mg (1.21 mmol, 64%) of the desired product. mp 107-108° C.

Workup

  1. temperatureAfter cooling
  2. filtrationfiltered through celite
  3. washrinsed thoroughly with ether
  4. customThe filtrate was evaporated to dryness
  5. customto give a brown residue
  6. customPurification by flash chromatography (silica gel, 5% EtOAc/hexane)

Sources & evidence

ORD record
ord-6255e458da4743dbb9845a756a0464eb
Source dataset
uspto-grants-2005_12
Patent number
US06972287B1

Reaction notes

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