1-Bromonaphthalene → 1-(1-Naphthyl)-2-(trimethylsilyl)acetylene

HRID 1837396Notes

Reaction equation

HRID 1837396 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][CH:3]=1.[CH3:12][Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14]>C(NC(C)C)(C)C.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.[Cu](I)I>[CH3:12][Si:13]([CH3:15])([CH3:14])[C:16]#[C:17][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 70011-BromonaphthaleneHCID 66111Trimethylsilylacetylene

Product 1

HCID 44382321-(1-Naphthyl)-2-(trimethylsilyl)acetyleneYield 88.9%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7912DiisopropylamineSolvent

Conditions

Temperature
80 °C

Procedure

Under an argon atmosphere, 50 g (0.241 mol) of 1-bromonaphthalene, 2.5 g (3.6 mmol) of bis(triphenylphosphine)palladium(II) dichloride and 0.68 g (3.6 mmol) of copper Iodide were dissolved in 500 ml of diisopropylamine in a 1 L 3-necked flask equipped with a stirrer, thermometer and reflux condenser. 35.6 g (0.362 mol) of trimethylsilyl acetylene was slowly dropped into the resulting mixture at room temperature. The reaction mixture was slowly heated to 80° C. and refluxed 12 hours. After the reaction was completed, the reaction mixture was cooled down to room temperature. The precipitated salt was filtered off, and the solvent was removed from the filtrate under a reduced pressure. The residue was dissolved in methylene chloride. The organic layer was washed with water several times and then dried with anhydrous magnesium sulfate. The solvent was removed, to obtain a liquid. The obtained liquid was purified by silica gel column chromatography using hexane as an eluent, to give a colorless viscous liquid. The liquid was recrystallized from ethanol to give white crystal in needle-shape. The white crystal was recovered and then sufficiently dried at room temperature, to give 48 g (88.9% yield) of the desired product having a melting point of 41-43° C.

Workup

  1. customequipped with a stirrer
  2. temperaturethermometer and reflux condenser
  3. temperaturerefluxed 12 hours
  4. temperaturethe reaction mixture was cooled down to room temperature
  5. filtrationThe precipitated salt was filtered off
  6. customthe solvent was removed from the filtrate under a reduced pressure
  7. dissolutionThe residue was dissolved in methylene chloride
  8. washThe organic layer was washed with water several times
  9. dry with materialdried with anhydrous magnesium sulfate
  10. customThe solvent was removed
  11. customto obtain a liquid
  12. customThe obtained liquid was purified by silica gel column chromatography
  13. customto give a colorless viscous liquid
  14. customThe liquid was recrystallized from ethanol
  15. customto give white crystal in needle-shape
  16. customThe white crystal was recovered
  17. customsufficiently dried at room temperature

Sources & evidence

ORD record
ord-a3a0a05566ce41259817f3f7146ae8ee
Source dataset
uspto-grants-2004_08
Patent number
US06780950B2

Reaction notes

Loading…