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

HRID 726131Notes

Reaction equation

HRID 726131 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 1.0M 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. customto reach to r.t.
  3. filtrationfiltered
  4. washThe filtrate was successively washed with 2N HCl, 5% sodium bicarbonate and brine
  5. customdried
  6. additionThe residue, a mixture of several products
  7. customobtained
  8. customafter evaporation of the solvent
  9. customwas chromatographed over silica gel (20% hexanes in dichloromethane)
  10. customthe major product (least polar) was isolated
  11. distillationfurther purified by kugelrohr distillation, b.p. 130°-140° C. (pot temperature)/12 mmHg

Sources & evidence

ORD record
ord-f590fd2e2f56437d9d582472148ef8c4
Source dataset
uspto-grants-1998_01
Patent number
US05708032

Reaction notes

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