Tri(butyl)vinyltin → 1-(2-Methoxy-4-nitrophenyl)-3-vinylpyridin-2(1H)-one

HRID 391730Notes

Reaction equation

HRID 391730 reaction equation
Br[C:2]1[C:3](=[O:19])[N:4]([C:8]2[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][C:9]=2[O:17][CH3:18])[CH:5]=[CH:6][CH:7]=1.[CH2:20](C([Sn])=C(CCCC)CCCC)[CH2:21]CC>O1CCOCC1>[CH3:18][O:17][C:9]1[CH:10]=[C:11]([N+:14]([O-:16])=[O:15])[CH:12]=[CH:13][C:8]=1[N:4]1[CH:5]=[CH:6][CH:7]=[C:2]([CH:20]=[CH2:21])[C:3]1=[O:19]

Participants

4

Reactant 2

HCID 53438229Tri(butyl)vinyltinHCID 594101453-Bromo-1-(2-methoxy-4-nitrophenyl)pyridin-2(1H)-one

Product 1

HCID 594101761-(2-Methoxy-4-nitrophenyl)-3-vinylpyridin-2(1H)-one

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

100 g (308 mmol) of the compound from Example 19A are dissolved in 1.4 l of anhydrous dioxane, and 8.9 g (7.7 mmol) of tetrakis(triphenylphospine)palladium and 117 g (370 mmol) of tributylvinyltin are added. The mixture is heated at reflux for 16 h. The reaction solution is then allowed to cool and filtered through kieselguhr. The filtrates are concentrated to dryness under reduced pressure. The residue is chromatographed on silica gel using a gradient of cyclohexane and ethyl acetate. The product-containing fractions are combined and concentrated to dryness under reduced pressure. Petroleum ether is added until crystallization sets in. The crystals are filtered off and dried under reduced pressure. This gives 37 g (41% of theory) of the desired product.

Workup

  1. temperatureThe mixture is heated
  2. temperatureat reflux for 16 h
  3. temperatureto cool
  4. filtrationfiltered through kieselguhr
  5. concentrationThe filtrates are concentrated to dryness under reduced pressure
  6. customThe residue is chromatographed on silica gel using a gradient of cyclohexane and ethyl acetate
  7. concentrationconcentrated to dryness under reduced pressure
  8. additionPetroleum ether is added until crystallization sets in
  9. filtrationThe crystals are filtered off
  10. customdried under reduced pressure

Sources & evidence

ORD record
ord-b2766cb001604a1f9e6dc43f63304cbc
Source dataset
uspto-grants-2013_02
Patent number
US08383822B2

Reaction notes

Loading…