Sodium Acetate → 4-(3-(3,5-Dichlorophenyl)-4,4,4-trifluoro-2-butenoyl)-2-methylbenzoic acid

HRID 645300Notes

Reaction equation

HRID 645300 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:23])[CH:9]=[C:10]([C:15]2[CH:20]=[C:19]([Cl:21])[CH:18]=[C:17]([Cl:22])[CH:16]=2)[C:11]([F:14])([F:13])[F:12])=[CH:4][C:3]=1[CH3:24].[C:25]([O-:28])(=[O:27])C.[Na+].[C]=O>COCCOC.O.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:22][C:17]1[CH:16]=[C:15]([C:10]([C:11]([F:14])([F:13])[F:12])=[CH:9][C:8]([C:5]2[CH:6]=[CH:7][C:2]([C:25]([OH:28])=[O:27])=[C:3]([CH3:24])[CH:4]=2)=[O:23])[CH:20]=[C:19]([Cl:21])[CH:18]=1

Participants

8

Reactant 3

HCID 517045Sodium AcetateHCID 765635821-(4-Bromo-3-methylphenyl)-3-(3,5-dichlorophenyl)-4,4,4-trifluoro-2-buten-1-oneHCID 178418416HCID 178418416, compound

Product 1

HCID 667352444-(3-(3,5-Dichlorophenyl)-4,4,4-trifluoro-2-butenoyl)-2-methylbenzoic acidYield 58.2%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a solution of 4.85 g of 1-(4-bromo-3-methylphenyl)-3-(3,5-dichlorophenyl)-4,4,4-trifluoro-2-butene-1-one representing mixed geometrical isomers (isomeric ratio of 8:1) that was synthesized according to Synthetic Examples 1 and 2 and 1.36 g of sodium acetate in 20 mL of 1,2-dimethoxyethane and 20 mL of water in an autoclave, 0.25 g of 1,1′-bis(diphenylphosphino) ferrocene and 50 mg of palladium(II) acetate were added, the mixture was stirred for 5.5 hours at 110° C. in an atmosphere of carbon monoxide at 1.0 MPa. After that, the temperature was cooled to room temperature to isolate solid matter by filtration, diluted hydrochloric acid was added to extract with ethyl acetate, and then an organic layer was dehydrated and dried with saturated saline followed by anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The resulting residue was purified using silica gel column chromatography that was eluted with ethyl acetate-hexane (1:5) followed by crystallization from a mixed solvent of hexane and a small amount of ethyl acetate to obtain 2.6 g of aimed product as white solid.

Workup

  1. customwas synthesized
  2. additionwere added
  3. customto isolate solid matter
  4. filtrationby filtration, diluted hydrochloric acid
  5. additionwas added
  6. extractionto extract with ethyl acetate
  7. customdried with saturated saline
  8. distillationthe solvent was distilled off under reduced pressure
  9. customThe resulting residue was purified
  10. washwas eluted with ethyl acetate-hexane (1:5)
  11. customfollowed by crystallization from a mixed solvent of hexane

Sources & evidence

ORD record
ord-262b3406d7ca4117b24ce37c49d15fc9
Source dataset
uspto-grants-2010_04
Patent number
US07700808B2

Reaction notes

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