Citric Acid → HCID 68957343, compound

HRID 2191796Notes

Reaction equation

HRID 2191796 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.Br[C:25]1[CH:30]=[CH:29][CH:28]=[C:27]([CH3:31])[C:26]=1[CH3:32].C(N(CCCC)CCCC)CCC.F[B-](F)(F)F.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.CN(C)C(=O)C>[CH3:32][C:26]1[C:27]([CH3:31])=[CH:28][CH:29]=[CH:30][C:25]=1/[CH:21]=[CH:20]/[C:18]1[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]2[CH:22]=[CH:23][C:2]([F:1])=[CH:3][CH:4]=2)[CH:19]=1

Participants

9

Reactant 5

HCID 311Citric AcidHCID 7622Tributylamine2×HCID 684723-Bromo-o-xylene2×HCID 44558591Tri-t-butylphosphine fluoroborate3×HCID 68959213Tert-butyl 2-(4-fluoroanilino)-4-vinylbenzoate

Product 1

HCID 68957343HCID 68957343, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalyst3×HCID 8857Ethyl AcetateSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
120 °C

Procedure

To N,N-dimethylacetamide 2.0 mL solution of tert-butyl 2-(4-fluoroanilino)-4-vinylbenzoate 0.10 g were added 3-bromo-o-xylene 0.064 mL, tributylamine 0.15 mL, palladium acetate 4.0 mg and tri-tert-butylphosphine tetrafluoroborate 3.0 mg at room temperature, and it was stirred under nitrogen atmosphere at 120° C. for 2 hours. Palladium acetate 4.0 mg and tri-tert-butylphosphine tetrafluoroborate 3.0 mg were added to it, and it was stirred under nitrogen atmosphere at 120° C. for 2 hours. 3-Bromo-o-xylene 0.064 mL, tributylamine 0.11 mL, palladium acetate 4.0 mg and tri-tert-butylphosphine tetrafluoroborate 3.0 mg were added to it, and it was stirred under nitrogen atmosphere at 120° C. for 5 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 sequential washing with 10% citric acid aqueous solution 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-((E)-2-(2,3-dimethylphenyl)vinyl)-2-(4-fluoroanilino)benzoate.

Workup

  1. stirringwas stirred under nitrogen atmosphere at 120° C. for 2 hours
  2. stirringwas stirred under nitrogen atmosphere at 120° C. for 5 hours
  3. temperatureAfter the reaction mixture was cooled to room temperature
  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
  8. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-b9cae914a163477b847cdf8ee3ff9d77
Source dataset
uspto-grants-2012_12
Patent number
US08327467B2

Reaction notes

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