Hydrochloric Acid → HCID 68960063, compound

HRID 2191837Notes

Reaction equation

HRID 2191837 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.[NH2:14][C:15]1[CH:27]=[C:26]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:25]=[CH:24][C:16]=1[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18].C(=O)([O-])[O-].[Cs+].[Cs+].Cl>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.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].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.C(OCC)(=O)C.C1(C)C=CC=CC=1>[C:5]1([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:7][C:2]([NH:14][C:15]2[CH:27]=[C:26]([C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)[CH:25]=[CH:24][C:16]=2[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])=[CH:3][CH:4]=1

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 71014-BromobiphenylHCID 10796Cesium carbonateHCID 58508425Tert-butyl 3-amino-[1,1'-biphenyl]-4-carboxylate

Product 1

HCID 68960063HCID 68960063, compoundYield 76.7%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalyst2×HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylCatalyst2×HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To toluene 3.0 mL solution of 4-bromobiphenyl 0.43 g were added 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 17 mg, tert-butyl 2-amino-4-phenylbenzoate 0.20 g, cesium carbonate 0.48 g, palladium acetate 1.7 mg and tris(dibenzylideneacetone)dipalladium(0) 6.8 mg at room temperature, and it was heated and refluxed for 5 hours and 40 minutes. 2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 17 mg, tris(dibenzylideneacetone)dipalladium(0) 6.8 mg and palladium acetate 1.7 mg were added to it, and it was heated and refluxed for 2 hours and 20 minutes. After the reaction mixture was cooled to room temperature, ethyl acetate and 1.0 mol/L hydrochloric acid 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 [Fuji SILYSIA Chemical Ltd., PSQ100B(spherical type), eluent; hexane:ethyl acetate=50:1] to give tert-butyl 2-((biphenyl-4-yl)amino)-4-phenylbenzoate 0.24 g of a pale yellow solid.

Workup

  1. temperatureit was heated
  2. temperaturerefluxed for 5 hours and 40 minutes
  3. temperaturewas heated
  4. temperaturerefluxed for 2 hours and 20 minutes
  5. customThe organic layer was separated
  6. customcollected
  7. dry with materialdried over anhydrous magnesium sulfate
  8. washafter washing with saturated sodium chloride aqueous solution
  9. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-d58b91daed704c429e1205709f636228
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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