3,4,4-Trifluoro-3-butenoyl chloride → HCID 21836481, compound

HRID 1739692Notes

Reaction equation

HRID 1739692 reaction equation
[F:1][C:2](=[C:7]([F:9])[F:8])[CH2:3][C:4](Cl)=[O:5].[CH2:10]([Mg]Cl)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>CCOCC.[Cu]I>[F:1][C:2](=[C:7]([F:9])[F:8])[CH2:3][C:4]([C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=1[CH3:10])=[O:5]

Participants

5

Reactant 2

HCID 109207893,4,4-Trifluoro-3-butenoyl chlorideHCID 178418336HCID 178418336, compound

Product 1

HCID 21836481HCID 21836481, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolvent2×

Procedure

To a solution of 3,4,4-trifluoro-3-butenoyl chloride (3.75 g, 23.65 mmol) in anhyd. ether (100 mL) was treated with copper(I)iodide (2.28 g, 12 mmol) followed by 24 mL of 1.0 M solution of benzylmagnesium chloride in ether dropwise at -78° C. with stirring under nitrogen. The reaction mixture was stirred at -78° C. for 10 min and allowed to reach to r.t and filtered. The filtrate was successively washed with 2N HCl, 5% sodium bicarbonate and brine, and dried. The residue, a mixture of several products, obtained after evaporation of the solvent was chromatographed over silica gel (20% hexanes in dichloromethane) and the major product (least polar) was isolated and further purified by kugelrohr distillation, b.p. 130-140° C. (pot temperature)/12 mmHg. Proton and fluorine NMR spectra of this material was found to correspond to the title compound.

Workup

  1. stirringThe reaction mixture was stirred at -78° C. for 10 min
  2. filtrationfiltered
  3. washThe filtrate was successively washed with 2N HCl, 5% sodium bicarbonate and brine
  4. customdried
  5. additionThe residue, a mixture of several products
  6. customobtained
  7. customafter evaporation of the solvent
  8. customwas chromatographed over silica gel (20% hexanes in dichloromethane)
  9. customthe major product (least polar) was isolated
  10. distillationfurther purified by kugelrohr distillation, b.p. 130-140° C. (pot temperature)/12 mmHg

Sources & evidence

ORD record
ord-a2c3549393324276a55c378afcab9820
Source dataset
uspto-grants-1999_10
Patent number
US05968916

Reaction notes

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