Citric Acid → HCID 67344113, compound

HRID 1673420Notes

Reaction equation

HRID 1673420 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[CH2:6].C(N(CCCC)CCCC)CCC.F[B-](F)(F)F.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.[C:41]([NH:49][C:50]1[CH:62]=[C:61](Br)[CH:60]=[CH:59][C:51]=1[C:52]([O:54][C:55]([CH3:58])([CH3:57])[CH3:56])=[O:53])(=[O:48])[C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1.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>[C:41]([NH:49][C:50]1[CH:62]=[C:61](/[CH:6]=[CH:5]/[C:4]2[CH:7]=[CH:8][CH:9]=[C:2]([Cl:1])[CH:3]=2)[CH:60]=[CH:59][C:51]=1[C:52]([O:54][C:55]([CH3:57])([CH3:58])[CH3:56])=[O:53])(=[O:48])[C:42]1[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=1

Participants

9

Reactant 5

HCID 311Citric AcidHCID 7622TributylamineHCID 14905m-Chlorostyrene2×HCID 44558591Tri-t-butylphosphine fluoroborate2×HCID 67343005Tert-butyl 2-(benzamido)-4-bromobenzoate

Product 1

HCID 67344113HCID 67344113, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalyst2×HCID 8857Ethyl AcetateSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
110 °C

Procedure

0.076 mL of 3-chlorostyrene, 0.19 mL of tributylamine, 2.9 mg of tri-tert-butylphosphine tetrafluoroborate and 4.5 mg of palladium acetate were added to 2.0 mL of N,N-dimethylacetamide solution containing 0.15 g of tert-butyl 2-(benzamido)-4-bromobenzoate at room temperature and stirred under nitrogen atmosphere at 110° C. for 4 hours and 30 minutes. After the reaction mixture was cooled to room temperature, 0.025 mL of 3-chlorostyrene, 2.9 mg of tri-tert-butylphosphine tetrafluoroborate and 4.5 mg of palladium acetate were added at room temperature and stirred under nitrogen atmosphere at 110° C. for 1 hour and 20 minutes. After the reaction mixture was cooled to room temperature, 10% citric acid aqueous solution and ethyl acetate were added. The organic layer was separated and dried over anhydrous magnesium sulfate after washed with 10% citric acid aqueous solution, a saturated sodium thiosulfate aqueous solution and a saturated sodium chloride aqueous solution sequentially, and the solvent was evaporated under reduced pressure. The obtained residue was purified with silica gel column chromatography [PSQ100B (spherical) manufactured by Fuji Silysia Chemical Ltd., eluent; hexane:ethyl acetate=10:1] to obtain 86 mg of tert-butyl 2-(benzamido)-4-((E)-2-(3-chlorophenyl)vinyl)benzoate as white solid.

Workup

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. stirringstirred under nitrogen atmosphere at 110° C. for 1 hour and 20 minutes
  3. temperatureAfter the reaction mixture was cooled to room temperature
  4. customThe organic layer was separated
  5. dry with materialdried over anhydrous magnesium sulfate
  6. washafter washed with 10% citric acid aqueous solution
  7. customa saturated sodium thiosulfate aqueous solution and a saturated sodium chloride aqueous solution sequentially, and the solvent was evaporated under reduced pressure
  8. customThe obtained residue was purified with silica gel column chromatography [PSQ100B (spherical) manufactured by Fuji Silysia Chemical Ltd., eluent; hexane:ethyl acetate=10:1]

Sources & evidence

ORD record
ord-eb947a5cad2a49afa83e7ab86a0a7632
Source dataset
uspto-grants-2011_08
Patent number
US07999132B2

Reaction notes

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