Citric Acid → HCID 68963147, compound

HRID 2191856Notes

Reaction equation

HRID 2191856 reaction equation
[NH2:1][C:2]1[CH:14]=[C:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:12]=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5].C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:28]1[CH:36]=[CH:35][CH:34]=[CH:33][C:29]=1[N:30]([CH3:32])[CH3:31].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>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].C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.C1(C)C=CC=CC=1>[CH3:31][N:30]([CH3:32])[C:29]1[CH:33]=[CH:34][CH:35]=[CH:36][C:28]=1[NH:1][C:2]1[CH:14]=[C:13]([C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)[CH:12]=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5]

Participants

10

Reactant 5

HCID 311Citric AcidHCID 10796Cesium carbonate2×HCID 1365272-Bromo-N,N-dimethylaniline2×HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl3×HCID 58508425Tert-butyl 3-amino-[1,1'-biphenyl]-4-carboxylate

Product 1

HCID 68963147HCID 68963147, compound

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalyst3×HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst3×HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

To toluene 3.0 mL suspension of tert-butyl 2-amino-4-phenylbenzoate 0.12 g and cesium carbonate 0.36 g were added 2-bromo-N,N-dimethylaniline 0.18 g, 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 11 mg, tris(dibenzylideneacetone)dipalladium(0) 4.1 mg and palladium acetate 2.0 mg at room temperature, and it was stirred at 110° C. for 24 hours. 2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 11 mg, tris(dibenzylideneacetone)dipalladium(0) 4.1 mg and palladium acetate 2.0 mg were added to it, and it was stirred at 110° C. for 21 hours. Cesium carbonate 73 mg, 2-bromo-N,N-dimethylaniline 45 mg, 2-dicyclohexylphosphino-2′,4′,6′-triisopropyl biphenyl 11 mg, tris(dibenzylideneacetone)dipalladium(0) 4.1 mg and palladium acetate 2.0 mg were added to it, and it was stirred at 110° C. for 24 hours. After the reaction mixture was cooled to room temperature, ethyl acetate and 10% citric acid aqueous solution were added to it, and insoluble matter was filtrated. The organic layer was separated and collected,dried over anhydrous magnesium sulfate after washing with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The obtained residue was refined by silica gel column chromatography [Trikonex company, Flash Tube 2008, eluent; hexane:ethyl acetate=10:1] to give tert-butyl 2-((2-(dimethylamino)phenyl)amino)-4-phenylbenzoate.

Workup

  1. stirringwas stirred at 110° C. for 21 hours
  2. stirringwas stirred at 110° C. for 24 hours
  3. temperatureAfter the reaction mixture was cooled to room temperature
  4. filtrationwas filtrated
  5. customThe organic layer was separated
  6. washafter washing with saturated sodium chloride aqueous solution
  7. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-f06231b55ddb4aaeb40330e71b1164ea
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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