Cesium carbonate → Tert-butyl 2-((3-(acetamido)phenyl)amino)-4-phenethylbenzoate

HRID 2191848Notes

Reaction equation

HRID 2191848 reaction equation
[NH2:1][C:2]1[CH:14]=[C:13]([CH2:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=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:30]1[CH:31]=[C:32]([NH:36][C:37](=[O:39])[CH3:38])[CH:33]=[CH:34][CH:35]=1.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.O.C(OCC)(=O)C.CC(O)(C)C>[C:37]([NH:36][C:32]1[CH:31]=[C:30]([NH:1][C:2]2[CH:14]=[C:13]([CH2:15][CH2:16][C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=3)[CH:12]=[CH:11][C:3]=2[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])[CH:35]=[CH:34][CH:33]=1)(=[O:39])[CH3:38]

Participants

10

Reactant 4

HCID 10796Cesium carbonate2×HCID 12123N-(3-Bromophenyl)acetamide2×HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl3×HCID 58508624Tert-butyl 2-amino-4-phenethylbenzoate

Product 1

HCID 68965181Tert-butyl 2-((3-(acetamido)phenyl)amino)-4-phenethylbenzoate

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalyst3×HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst3×HCID 962WaterSolventHCID 6386tert-ButanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To 2-methyl-2-propanol 2.5 mL solution of tert-butyl 2-amino-4-phenethylbenzoate 0.12 g were added cesium carbonate 0.26 g, N-(3-bromophenyl)acetamide 0.13 g, 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 10 mg, tris(dibenzylideneacetone)dipalladium(0) 4.0 mg and palladium acetate 2.0 mg at room temperature, and it was stirred at 80° C. for 4 hours. Tris(dibenzylideneacetone)dipalladium(0) 4.0 mg, palladium acetate 2.0 mg and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 10 mg were added to it, and it was stirred at 80° C. for 12 hours. Cesium carbonate 0.26 g, N-(3-bromophenyl)acetamide 0.13 g, 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 10 mg, tris(dibenzylideneacetone)dipalladium(0) 4.0 mg and palladium acetate 2.0 mg were added to it, and it was stirred at 80° C. for 5 hours and 30 minutes. After the reaction mixture was cooled to room temperature, ethyl acetate and water 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=2:1] to give tert-butyl 2-((3-(acetamido)phenyl)amino)-4-phenethylbenzoate.

Workup

  1. stirringwas stirred at 80° C. for 12 hours
  2. stirringwas stirred at 80° C. for 5 hours and 30 minutes
  3. temperatureAfter the reaction mixture was cooled to room temperature
  4. customThe organic layer was separated
  5. washafter washing with saturated sodium chloride aqueous solution
  6. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-6818c42a65404a28bd6e9b2edc4eb660
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

Loading…