Stannane, tributyl(1-ethoxyethenyl)- → 2-(1-Ethoxy-ethenyl)-5-fluoro-6-methyl-pyridine

HRID 406272Notes

Reaction equation

HRID 406272 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[C:4]([CH3:9])[N:3]=1.[CH2:10]([O:12][C:13]([Sn](CCCC)(CCCC)CCCC)=[CH2:14])[CH3:11]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[CH2:13]([O:12][C:10]([C:2]1[CH:7]=[CH:6][C:5]([F:8])=[C:4]([CH3:9])[N:3]=1)=[CH2:11])[CH3:14]

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 27831806-Bromo-3-fluoro-2-methylpyridine

Product 1

HCID 673246662-(1-Ethoxy-ethenyl)-5-fluoro-6-methyl-pyridine

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 2-bromo-5-fluoro-6-methylpyridine (25 g, 132 mmol), 1-ethoxyvinyltri-n-butyltin (48.9 ml, 145 mmol) and bis(triphenylphosphine)palladium (II) chloride (4.62 g, 6.58 mmol) in 1,4-dioxane (250 ml) was heated to 100° C. under nitrogen over night. The reaction was then cooled to room temperature and the solvent was removed in vacuo. The residue was purified by silica gel chromatography (eluted with a gradient of ethyl acetate in hexanes) to give the product 2-(1-ethoxy-ethenyl)-5-fluoro-6-methyl-pyridine, together with an unidentified impurity. This product was used in the next step. 1H NMR (500 MHz, CDCl3): δ 7.51 (dd, 1H), 7.28 (t, 1H), 5.33 (d, 1H), 4.31 (d, 1H), 3.96 (q, 2H), 2.53 (d, 3H), 1.43 (t, 3H).

Workup

  1. temperatureThe reaction was then cooled to room temperature
  2. customthe solvent was removed in vacuo
  3. customThe residue was purified by silica gel chromatography (
  4. washeluted with a gradient of ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-f750d7a9032e442aa6c1fb9f3326a25d
Source dataset
uspto-grants-2014_06
Patent number
US08754099B2

Reaction notes

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