Citric Acid → HCID 68964495, compound

HRID 2191637Notes

Reaction equation

HRID 2191637 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:5]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])=[C:4]([N+:15]([O-:17])=[O:16])[CH:3]=1.[NH:18]1[C:26]2[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH2:20][CH2:19]1.C(=O)([O-])[O-].[Cs+].[Cs+].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>[N:18]1([C:2]2[CH:14]=[CH:13][C:5]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])=[C:4]([N+:15]([O-:17])=[O:16])[CH:3]=2)[C:26]2[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH2:20][CH2:19]1

Participants

9

Reactant 4

HCID 311Citric AcidHCID 10328IndolineHCID 10796Cesium carbonateHCID 26369829tert-Butyl 4-bromo-2-nitrobenzoate

Product 1

HCID 68964495HCID 68964495, compound

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalyst2×HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To toluene 30 mL solution of tert-butyl 4-bromo-2-nitrobenzoate 3.0 g were added indoline 2.1 mL, cesium carbonate 8.0 g,2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 0.29 g, tris(dibenzylideneacetone)dipalladium(0) 0.11 g and palladium acetate 55 mg at room temperature, and it was heated and refluxed under nitrogen atmosphere for 3 hours and 30 minutes. After the reaction mixture was cooled to room temperature,2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 0.29 g, tris(dibenzylideneacetone)dipalladium(0) 0.11 g and palladium acetate 55 mg were added to it, and it was heated and refluxed under nitrogen atmosphere for 3 hours. After the reaction mixture was cooled to room temperature, 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. Toluene was added to the obtained residue,dried over anhydrous magnesium sulfate after sequential washing with 1.0 mol/L hydrochloric acid and saturated sodium chloride aqueous solution, 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=10:1] to give tert-butyl 4-(indolin-1-yl)-2-nitrobenzoate 2.0 g of yellow solid.

Workup

  1. temperatureit was heated
  2. temperaturerefluxed under nitrogen atmosphere for 3 hours and 30 minutes
  3. additionwere added to it, and it
  4. temperaturewas heated
  5. temperaturerefluxed under nitrogen atmosphere for 3 hours
  6. customThe organic layer was separated
  7. washafter washing with saturated sodium chloride aqueous solution
  8. customthe solvent was removed under reduced pressure
  9. additionToluene was added to the obtained
  10. washafter sequential washing with 1.0 mol/L hydrochloric acid and saturated sodium chloride aqueous solution
  11. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-c1d71cba853e4e58acd690672e30bc96
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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