Pyridine → [(4-Methoxyphenyl)ethynyl](trimethyl)silane

HRID 1700825Notes

Reaction equation

HRID 1700825 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1.[CH3:10][Si:11]([C:14]#[CH:15])([CH3:13])[CH3:12].N1C=CC=CC=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I.CCCCCC.C(OCC)(=O)C>[CH3:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([C:15]#[C:14][Si:11]([CH3:13])([CH3:12])[CH3:10])=[CH:3][CH:4]=1

Participants

7

Reactant 3

HCID 1049PyridineHCID 77304-BromoanisoleHCID 66111Trimethylsilylacetylene

Product 1

HCID 3497861[(4-Methoxyphenyl)ethynyl](trimethyl)silaneYield 65%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 21226206Ethyl acetate hexaneSolvent

Conditions

Temperature
60 °C

Procedure

p-Bromoanisole(3.74 g, 20 mmol), tetrakis(triphenylphosphine)palladium (1.16 g, 1 mmol) and CuI (0.381 g, 2 mmol) were placed in a 100 mL three neck round bottom flask, equipped with a pressure equalizing addition funnel and a reflux condenser which was connected to a vacuum line. The third neck of the flask was sealed with a rubber septum. The apparatus was purged with nitrogen three times. Pyridine, (30 mL) was added and the mixture was stirred until it became a single clear phase. Trimethylsilyl-acetylene (1.96 g, 20 mmol) and 20 mL of pyridine were placed in the addition funnel and the solution was added dropwise to the reaction mixture at 45° C. The reaction mixture was heated to 60° C. The progress of the reaction was monitored by TLC (silica gel with hexane/ethyl acetate). When the reaction was complete, it was extracted with ether. The organic solution was dried over anhydrous magnesium sulfate, filtered and the volatile solvents removed by evaporation under reduced pressure. The residue was purified by column chromatography (silica gel with hexane/ethyl acetate). In this way, 2.66g, 65% yield, was obtained. 1H NMR δ: 7.39(d, 2H, J=8.75 Hz), 6.80(d, 2H, J=8.75 Hz), 3.78(s, 3H), 0.23(s, 9H).

Workup

  1. customequipped with a pressure
  2. additionaddition funnel and a reflux condenser which
  3. customThe third neck of the flask was sealed with a rubber septum
  4. customThe apparatus was purged with nitrogen three times
  5. additionPyridine, (30 mL) was added
  6. additionthe solution was added dropwise to the reaction mixture at 45° C
  7. extractionit was extracted with ether
  8. dry with materialThe organic solution was dried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. customthe volatile solvents removed by evaporation under reduced pressure
  11. customThe residue was purified by column chromatography (silica gel with hexane/ethyl acetate)
  12. customIn this way, 2.66g, 65% yield, was obtained

Sources & evidence

ORD record
ord-e29c5b2bc5184b1f81eab3e253b30468
Source dataset
uspto-grants-2002_02
Patent number
US06350875B1

Reaction notes

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