4-Bromotoluene → HCID 86591176, compound

HRID 1837397Notes

Reaction equation

HRID 1837397 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.[CH3:9][Si:10]([C:13]#[CH:14])([CH3:12])[CH3:11]>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>[CH3:9][Si:10]([CH3:12])([CH3:11])[C:13]1[CH:3]=[CH:4][C:5]([CH3:8])=[C:6]([C:7]#[CH:2])[CH:14]=1

Participants

6

Reactant 2

HCID 78054-BromotolueneHCID 66111Trimethylsilylacetylene

Product 1

HCID 86591176HCID 86591176, compoundYield 99.3%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7912DiisopropylamineSolvent

Conditions

Temperature
80 °C

Procedure

Under an argon atmosphere, 33 g (0.193 mol) of 4-bromotoluene, 2.7 g (3.85 mmol) of bis(triphenylphosphine)palladium(II) dichloride and 0.735 mg (3.85 mmol) of copper Iodide were put into a 1 L 3-necked flask equipped with a stirrer, thermometer and reflux condenser, and dissolved in 500 ml of diisopropylamine. 37.9 g (0.385 mol) of trimethylsilyl acetylene was slowly dropped into the resluting solution 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. The precipitated salt was filtered off, and then the solvent was removed under a reduced pressure. The residue was dissolved in methylene chloride. The organic solution was washed with water several times and then dried with anhydrous magnesium sulfate. The solvent was removed to obtain liquid, which was purified by silica gel column chromatography using hexane as an eluent, to give 35 g (99.3% yield) of pale brown viscous liquid.

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 solution was washed with water several times
  9. dry with materialdried with anhydrous magnesium sulfate
  10. customThe solvent was removed
  11. customto obtain liquid, which
  12. customwas purified by silica gel column chromatography

Sources & evidence

ORD record
ord-a8b228ec40f345c3bf89ce6478684c3f
Source dataset
uspto-grants-2004_08
Patent number
US06780950B2

Reaction notes

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