Cesium carbonate → tert-butyl 4-((E)-2-(2,3-dihydrobenzo[1,4]dioxin-6-yl)vinyl)-2-(4-fluoroanilino)benzoate

HRID 2191725Notes

Reaction equation

HRID 2191725 reaction equation
[F:1][C:2]1[CH:23]=[CH:22][C:5]([NH:6][C:7]2[CH:19]=[C:18]([CH:20]=[CH2:21])[CH:17]=[CH:16][C:8]=2[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])=[CH:4][CH:3]=1.I[C:25]1[CH:34]=[CH:33][C:28]2[O:29][CH2:30][CH2:31][O:32][C:27]=2[CH:26]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1>[O:29]1[C:28]2[CH:33]=[CH:34][C:25](/[CH:21]=[CH:20]/[C:18]3[CH:17]=[CH:16][C:8]([C:9]([O:11][C:12]([CH3:15])([CH3:13])[CH3:14])=[O:10])=[C:7]([NH:6][C:5]4[CH:22]=[CH:23][C:2]([F:1])=[CH:3][CH:4]=4)[CH:19]=3)=[CH:26][C:27]=2[O:32][CH2:31][CH2:30]1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 27761766-Iodo-2,3-dihydro-1,4-benzodioxineHCID 68959213Tert-butyl 2-(4-fluoroanilino)-4-vinylbenzoate

Product 1

HCID 68963963tert-butyl 4-((E)-2-(2,3-dihydrobenzo[1,4]dioxin-6-yl)vinyl)-2-(4-fluoroanilino)benzoate

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

To toluene 3.0 mL solution of tert-butyl 2-(4-fluoroanilino)-4-vinylbenzoate 0.12 g were added 2,3-dihydro-6-iodobenzo[1,4]dioxin 0.20 g, cesium carbonate 0.25 g, tetrabutylammonium bromide 37 mg and polymer-carried bis(acetato)triphenylphosphine palladium(II) 58 mg at room temperature, and it was stirred at 110° C. for 24 hours. After the reaction mixture was cooled to room temperature, insoluble matter was filtrated, 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 sequential washing with 10% citric acid aqueous solution and saturated sodium chloride aqueous solution,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=4:1] to give tert-butyl 4-((E)-2-(2,3-dihydrobenzo[1,4]dioxin-6-yl)vinyl)-2-(4-fluoroanilino)benzoate.

Workup

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. filtrationinsoluble matter was filtrated
  3. additionethyl acetate and 10% citric acid aqueous solution were added to it
  4. customThe organic layer was separated
  5. customcollected
  6. dry with materialdried over anhydrous magnesium sulfate
  7. washafter sequential washing with 10% citric acid aqueous solution and saturated sodium chloride aqueous solution,the solvent
  8. customwas removed under reduced pressure

Sources & evidence

ORD record
ord-3f52de3e990b43c7a499aafea7f2d831
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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