Ethanol → 3-Ethenyl-2,6-difluorobenzonitrile

HRID 2175835Notes

Reaction equation

HRID 2175835 reaction equation
FC(F)(F)S(O[C:7]1[CH:12]=[CH:11][C:10]([F:13])=[C:9]([C:14]#[N:15])[C:8]=1[F:16])(=O)=O.[CH2:19](O)[CH3:20]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[CH:19]([C:7]1[C:8]([F:16])=[C:9]([C:10]([F:13])=[CH:11][CH:12]=1)[C:14]#[N:15])=[CH2:20]

Participants

4

Reactant 2

HCID 702EthanolHCID 867270593-Cyano-2,4-difluorophenyl trifluoromethanesulfonate

Product 1

HCID 867270603-Ethenyl-2,6-difluorobenzonitrile

Reagents, catalysts & solvents 1

HCID 178418807HCID 178418807, compoundCatalyst

Procedure

3-Cyano-2,4-difluorophenyl trifluoromethanesulfonate (5.20 g, 18.1 mmol), potassium vinyl trifluoroborate (4.85 g, 36.2 mmol), PdCl2(dppf)-CH2Cl2 Adduct (0.662 g, 0.905 mmol), and TEA (5.05 mL, 36.2 mmol) were added to 75 mL of ethanol. The reaction mixture was degassed then heated at reflux for 4 h. LC-MS analysis confirmed product peak. The reaction mixture was diluted with ethyl acetate, washed twice with brine, dried, and evaporated to dryness. The crude material was then purified by MPLC chromatography through a 330 g Redi-sep column eluting with 10% EtOAc/Hexane solvent system to yield 3-ethenyl-2,6-difluorobenzonitrile.

Workup

  1. customThe reaction mixture was degassed
  2. temperaturethen heated
  3. temperatureat reflux for 4 h
  4. additionThe reaction mixture was diluted with ethyl acetate
  5. washwashed twice with brine
  6. customdried
  7. customevaporated to dryness
  8. customThe crude material was then purified by MPLC chromatography through a 330 g Redi-sep column
  9. washeluting with 10% EtOAc/Hexane solvent system

Sources & evidence

ORD record
ord-757af68304c14e249a9cf72079d3ce52
Source dataset
uspto-grants-2015_06
Patent number
US09062070B2

Reaction notes

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