Cesium carbonate → HCID 68962009, compound

HRID 2191823Notes

Reaction equation

HRID 2191823 reaction equation
[NH2:1][C:2]1[CH:14]=[C:13]([N:15]2[C:23]3[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=3)[CH2:17][CH2:16]2)[CH:12]=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5].Br[C:25]1[CH:30]=[CH:29][C:28]2[O:31][CH2:32][O:33][C:27]=2[CH:26]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1>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.C1(C)C=CC=CC=1>[O:31]1[C:28]2[CH:29]=[CH:30][C:25]([NH:1][C:2]3[CH:14]=[C:13]([N:15]4[C:23]5[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=5)[CH2:17][CH2:16]4)[CH:12]=[CH:11][C:3]=3[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])=[CH:26][C:27]=2[O:33][CH2:32]1

Participants

8

Reactant 4

HCID 10796Cesium carbonate2×HCID 758311-Bromo-3,4-(methylenedioxy)benzene2×HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl4×HCID 68957351Tert-butyl 2-amino-4-(indolin-1-yl)benzoate

Product 1

HCID 68962009HCID 68962009, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalyst4×HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst4×HCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

To toluene 3.0 mL solution of tert-butyl 2-amino-4-(indolin-1-yl)benzoate 0.12 g were added 1-bromo-3,4-methylenedioxybenzene 0.12 mL, cesium carbonate 0.26 g, tris(dibenzylideneacetone)dipalladium(0) 3.7 mg, palladium acetate 1.8 mg and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 9.5 mg at room temperature, and it was stirred at 110° C. for 6 hours. Tris(dibenzylideneacetone)dipalladium(0) 3.7 mg, palladium acetate 1.8 mg and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 9.5 mg were added at room temperature, and it was stirred at 110° C. for 18 hours 30 minutes. 1-Bromo-3,4-methylenedioxybenzene 0.12 mL, cesium carbonate 0.26 g, tris(dibenzylideneacetone)dipalladium(0) 3.7 mg, palladium acetate 1.8 mg and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 9.5 mg were added to it, and it was stirred at 110° C. for 22 hours. After the reaction mixture was cooled to room temperature, tris(dibenzylideneacetone)dipalladium(0) 3.7 mg, palladium acetate 1.8 mg and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 9.5 mg were added to it, and it was stirred at 110° C. for 20 hours. After the reaction mixture was cooled to room temperature, insoluble matter was filtrated, and ethyl acetate and 10% citric acid aqueous solution were added to it. 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-((benzo-1,3-dioxol-5-yl)amino)-4-(indolin-1-yl)benzoate.

Workup

  1. stirringit was stirred at 110° C. for 18 hours 30 minutes
  2. stirringwas stirred at 110° C. for 22 hours
  3. temperatureAfter the reaction mixture was cooled to room temperature
  4. stirringwas stirred at 110° C. for 20 hours
  5. temperatureAfter the reaction mixture was cooled to room temperature
  6. filtrationinsoluble matter was filtrated
  7. additionethyl acetate and 10% citric acid aqueous solution were added to it
  8. customThe organic layer was separated
  9. washafter washing with saturated sodium chloride aqueous solution
  10. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-4f0cbfc48ede417799010d0c5d42b333
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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