Trimethylsilylacetylene → 1,4-Bis(trimethylsilylethynyl)-2,5-dimethoxybenzene

HRID 7197

Reaction equation

HRID 7197 reaction equation
Br[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5](Br)=[CH:4][C:3]=1[O:11][CH3:12].[CH3:13][Si:14]([C:17]#[CH:18])([CH3:16])[CH3:15]>C(NC(C)C)(C)C.[Cu](I)I>[CH3:13][Si:14]([C:17]#[C:18][C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([C:18]#[C:17][Si:14]([CH3:16])([CH3:15])[CH3:13])=[CH:4][C:3]=1[O:11][CH3:12])([CH3:16])[CH3:15]

Participants

5

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 2312401,4-Dibromo-2,5-dimethoxybenzene

Product 1

HCID 105925721,4-Bis(trimethylsilylethynyl)-2,5-dimethoxybenzeneYield 73.8%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 7912DiisopropylamineSolvent

Conditions

Temperature
80 °C

Procedure

100 g (0.338 mol) of 1,4-dibromo-2,5-dimethoxybenzene, 7.12 g (0.01 mol) of bistriphenylphospine palladium dichloride and 1.93 g (0.01 mol) of copper iodide were put into a 1 litter 3-neck round-bottom flask equipped with a stirrer, a thermometer and a reflux condenser under an argon atmosphere, and dissolved in 600 ml of diisopropylamine. 99 g (1 mol) of trimethylsilylacetylene was then slowly added dropwise at room temperature, and stirred at 80° C. for 12 hours. When the reaction was completed, the reaction mixture was cooled down to room temperature, generated salt was filtered off, and then the solvent was removed under a reduced pressure. The residue was dissolved in chloroform, and resultant was washed with water several times and then dried with anhydrous magnesium sulfate, which was then filtered off. The solvent was removed, and the residue was recrystallized from ethyl acetate/hexane mixture to obtain pale yellow crystal, which was sufficiently dried in a vacuum oven at 40° C. to give 82.5 g (yield: 73%) of the desired product, and its melting point was 164° C.–165° C.

Workup

  1. customequipped with a stirrer
  2. temperaturethe reaction mixture was cooled down to room temperature
  3. filtrationwas filtered off
  4. customthe solvent was removed under a reduced pressure
  5. dissolutionThe residue was dissolved in chloroform
  6. washresultant was washed with water several times
  7. dry with materialdried with anhydrous magnesium sulfate, which
  8. filtrationwas then filtered off
  9. customThe solvent was removed
  10. customthe residue was recrystallized from ethyl acetate/hexane mixture
  11. customto obtain pale yellow crystal, which
  12. customwas sufficiently dried in a vacuum oven at 40° C.

Sources & evidence

ORD record
ord-055226509f2c42309f67211cf933f618
Source dataset
uspto-grants-2006_08
Patent number
US07084231B2

Linked notes

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