Cesium carbonate → Tert-butyl 2-((2,3-dihydrobenzo[1,4]dioxin-6-yl)amino)-4-phenylbenzoate

HRID 2191709Notes

Reaction equation

HRID 2191709 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].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].I[C:74]1[CH:83]=[CH:82][C:77]2[O:78][CH2:79][CH2:80][O:81][C:76]=2[CH:75]=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1>[O:78]1[C:77]2[CH:82]=[CH:83][C:74]([NH:1][C:2]3[CH:14]=[C:13]([C:15]4[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=4)[CH:12]=[CH:11][C:3]=3[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])=[CH:75][C:76]=2[O:81][CH2:80][CH2:79]1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 634876Binap, (A+-)-2×HCID 27761766-Iodo-2,3-dihydro-1,4-benzodioxineHCID 58508425Tert-butyl 3-amino-[1,1'-biphenyl]-4-carboxylate

Product 1

HCID 68959355Tert-butyl 2-((2,3-dihydrobenzo[1,4]dioxin-6-yl)amino)-4-phenylbenzoate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalyst2×HCID 1140TolueneSolvent

Procedure

To toluene 3.0 mL suspension of tert-butyl 2-amino-4-phenylbenzoate 0.10 g, rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl 2.3 mg, palladium acetate 0.8 mg and cesium carbonate 0.24 g was added 2,3-dihydro-6-iodobenzo[1,4]dioxin 0.24 g, and it was heated and refluxed for 24 hours. After the reaction mixture was cooled to room temperature, rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl 2.3 mg and palladium acetate 0.8 mg were added, and it was heated and refluxed for 24 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-((2,3-dihydrobenzo[1,4]dioxin-6-yl)amino)-4-phenylbenzoate.

Workup

  1. temperaturewas heated
  2. temperaturerefluxed for 24 hours
  3. temperatureit was heated
  4. temperaturerefluxed for 24 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-e38f5e611d544a249e39fa5f4a3ef7c2
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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