Trimethylsilylacetylene → HCID 23497953, compound

HRID 1837393Notes

Reaction equation

HRID 1837393 reaction equation
Br[C:2]1[C:3]2[C:8]([CH:9]=[C:10]3[C:15]=1[CH:14]=[CH:13][CH:12]=[CH:11]3)=[CH:7][CH:6]=[CH:5][CH:4]=2.[CH3:16][Si:17]([C:20]#[CH:21])([CH3:19])[CH3:18]>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>[CH3:16][Si:17]([CH3:19])([CH3:18])[C:20]1[C:4]2[C:3]([CH:2]=[C:15]3[C:21]=1[C:11]([C:10]#[CH:9])=[CH:12][CH:13]=[CH:14]3)=[CH:8][CH:7]=[CH:6][CH:5]=2

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 740629-Bromoanthracene

Product 1

HCID 23497953HCID 23497953, compoundYield 83.3%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7912DiisopropylamineSolvent

Conditions

Temperature
80 °C

Procedure

Under an argon atmosphere, 40 g (0.155 mol) of 9-bromoanthracene, 3.3 g (4.6 mmol) of bis(triphenylphosphine)palladium(II) dichloride and 0.87 g (3 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. 23 g (0.233 mol) of trimethylsilyl acetylene was then slowly dropped into the resulting mixture at room temperature. The reaction mixture was slowly heated to 80° C. and refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled down to room temperature, and then the precipitated salt was filtered off. The solvent was removed under a reduced pressure, and then 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 orange-colored liquid, which was purified by silica gel column chromatography using hexane as an eluent, and then recrystallized from ethanol to give yellow crystal. The yellow crystal was recovered and sufficiently dried in a vacuum oven at 40° C., to give 32 g (83.3% yield) of the desired product having a melting point of 66-68° C.

Workup

  1. customequipped with a stirrer
  2. temperaturethermometer and reflux condenser
  3. temperaturerefluxed for 12 hours
  4. temperaturethe reaction mixture was cooled down to room temperature
  5. filtrationthe precipitated salt was filtered off
  6. customThe solvent was removed 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 orange-colored liquid, which
  12. customwas purified by silica gel column chromatography
  13. customrecrystallized from ethanol
  14. customto give yellow crystal
  15. customThe yellow crystal was recovered
  16. customsufficiently dried in a vacuum oven at 40° C.

Sources & evidence

ORD record
ord-159fae7e626e4977880e324df8cc6723
Source dataset
uspto-grants-2004_08
Patent number
US06780950B2

Reaction notes

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