Tributylvinyltin → HCID 86668301, compound

HRID 75093Notes

Reaction equation

HRID 75093 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[N:5]=[C:4]([C:9]([O:11][CH3:12])=[O:10])[C:3]=1I.[CH:14]([Sn](CCCC)(CCCC)CCCC)=[CH2:15]>ClCCCl.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[N:5]=[C:4]([C:9]([O:11][CH3:12])=[O:10])[C:3]=1[CH:14]=[CH2:15]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 86668299HCID 86668299, compound

Product 1

HCID 86668301HCID 86668301, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 111,2-DichloroethaneSolvent

Procedure

Methyl 4,6-dichloro-3-iodopicolinate (0.56 g, 1.7 mmol), vinyltributylstannane (580 μl, 0.63 g, 2.0 mmol) and bis(triphenylphosphine)palladium(II) chloride (0.12 g, 0.17 mmol) were combined in 1,2-dichloroethane (8 mL) and the mixture was sparged with a stream of nitrogen for 15 min. The reaction mixture was stirred at reflux for 21 h, cooled to room temperature, and diluted with ethyl acetate (15 mL). A solution of 20% KHF2 (10 ml) was added and the mixture was stirred for 45 minutes. The mixture was filtered through Celite. The organic phase was washed with water, washed with saturated sodium chloride, dried over sodium sulfate, and concentrated under vacuum. The crude product was purified by flash chromatography (SiO2, ethyl acetate/hexanes) to afford the title compound as a solid (0.30 g, 70%): 1H NMR (400 MHz, CDCl3) δ 7.50 (s, 1H), 6.82 (ddd, J=17.8, 11.5, 1.7 Hz, 1H), 5.66 (dd, J=11.4, 8.1 Hz, 1H), 5.55 (dt, J=17.7, 5.0 Hz, 1H), 3.92 (s, 3H); EIMS m/z 231.

Workup

  1. customthe mixture was sparged with a stream of nitrogen for 15 min
  2. temperatureat reflux for 21 h
  3. additiondiluted with ethyl acetate (15 mL)
  4. additionA solution of 20% KHF2 (10 ml) was added
  5. stirringthe mixture was stirred for 45 minutes
  6. filtrationThe mixture was filtered through Celite
  7. washThe organic phase was washed with water
  8. washwashed with saturated sodium chloride
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated under vacuum
  11. customThe crude product was purified by flash chromatography (SiO2, ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-d2a30c93cda94a91a227a38b132d5e20
Source dataset
uspto-grants-2014_09
Patent number
US08835409B2

Reaction notes

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