Tributylvinyltin → 4-Methyl-2-vinylpyridine

HRID 1827492Notes

Reaction equation

HRID 1827492 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][N:3]=1.[CH2:9]([Sn](CCCC)(CCCC)C=C)[CH2:10]CC>C1(C)C=CC=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>[CH3:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([CH:9]=[CH2:10])[CH:7]=1

Participants

6

Reactant 2

HCID 81998TributylvinyltinHCID 27340872-Bromo-4-methylpyridine

Product 1

HCID 112057414-Methyl-2-vinylpyridineYield 53%

Reagents, catalysts & solvents 3

HCID 314042,6-Di-tert-butyl-4-methylphenolCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A yellow mixture of 2-bromo-4-methyl-pyridine (Aldrich, 5.2 9, 30.5 mmol, 1.0 eq), 2,6-di-tert-butyl-4-methyl-phenol (Aldrich, 67 mg, 0.3 mmol, 1 mol %), tributyl-vinyl-stannane (Aldrich, 26.8 mL, 91.5 mmol, 3.0 eq) and tetrakis(triphenylphosphine) palladium (0) (Strem, 1.8 9, 1.5 mmol, 5 mol %) in toluene (100 mL) was degassed and purged with argon. An amber solution was obtained after the mixture was warmed to 100° C. The reaction mixture was quenched after 18 hours by the addition of 1.0 M HCl. The acidic extract was washed with ether, adjusted to pH 9 with solid sodium bicarbonate, and extracted with ethyl acetate. The organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude product (3.7 g of a brown oil) was purified by flash chromatography (silica) and eluted with 0–5% ethyl acetate-dichloromethane, which gave a clear oil (1.9 g, 53%). 1H NMR (DMSO-d6, 300 MHz) δ 8.39 (1H, d, J=4.9 Hz), 7.33 (1H, s), 7.10 (1H, dd, J=5.0, 0.8 Hz), 6.77 (1H, dd, 17.5, 10.8 Hz), 6.20 (1H, dd, J=17.5, 1.7 Hz), 5.44 (1H, dd, J=10.8, 1.8 Hz), 2.31 (3H, s). ESIMS m/z 120 (M+H)+.

Workup

  1. customwas degassed
  2. custompurged with argon
  3. customAn amber solution was obtained after the mixture
  4. customThe reaction mixture was quenched after 18 hours by the addition of 1.0 M HCl
  5. extractionThe acidic extract
  6. washwas washed with ether
  7. extractionextracted with ethyl acetate
  8. washThe organic extracts were washed with brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe crude product (3.7 g of a brown oil) was purified by flash chromatography (silica)
  13. washeluted with 0–5% ethyl acetate-dichloromethane, which

Sources & evidence

ORD record
ord-753577577dad4faeaf8dec6be43f749f
Source dataset
uspto-grants-2006_05
Patent number
US07053107B2

Reaction notes

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