Nitrogen → 2-Fluoro-3-trifluoromethyl-4-vinylaniline

HRID 1811532

Reaction equation

HRID 1811532 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([F:9])[C:3]=1[C:10]([F:13])([F:12])[F:11].[CH2:14](C([Sn](Cl)(Cl)Cl)=C(CCCC)CCCC)[CH2:15]CC.N#N>CN(C=O)C>[F:9][C:4]1[C:3]([C:10]([F:13])([F:12])[F:11])=[C:2]([CH:14]=[CH2:15])[CH:8]=[CH:7][C:5]=1[NH2:6]

Participants

5

Reactant 3

HCID 947NitrogenHCID 536697144-Bromo-2-fluoro-3-(trifluoromethyl)anilineHCID 86633508Tributylvinyltin chloride

Product 1

HCID 688215442-Fluoro-3-trifluoromethyl-4-vinylaniline

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

4-Bromo-2-fluoro-3-trifluoromethylaniline described above (5.0 g, 19.4 mmol) and tributylvinyltin chloride (7.1 g, 20.4 mmol) are added to anhydrous DMF (100 mL). The solution is degassed with N2, palladium tetrakistriphenylphosphine (1.5 g, 1.3 mmol) is added, and the reaction is heated at 120° C. for 18 hours. After cooling, the reaction mixture is partitioned between Et2O and saturated aqueous NaCl. The separated ether layer is washed with fresh saturated aqueous NaCl (2×), dried with Na2SO4, and concentrated under reduced pressure. The residue is purified by flash chromatography eluting with 5, then 10, then 20% EtOAc in hexanes to give the desired product, 2-fluoro-3-trifluoromethyl-4-vinylaniline.

Workup

  1. additionis added
  2. temperatureAfter cooling
  3. customthe reaction mixture is partitioned between Et2O and saturated aqueous NaCl
  4. washThe separated ether layer is washed with fresh saturated aqueous NaCl (2×)
  5. dry with materialdried with Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customThe residue is purified by flash chromatography
  8. washeluting with 5

Sources & evidence

ORD record
ord-b23fb36a00544ed0bba69c20bf831d51
Source dataset
uspto-grants-2013_01
Patent number
US08362294B2

Linked notes

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