Triethylamine → 4-Chloro-3-methoxyphenylethynyl-trimethylsilane

HRID 17099Notes

Reaction equation

HRID 17099 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([Cl:10])=[C:6]([O:8][CH3:9])[CH:7]=1.[CH3:11][Si:12]([C:15]#[CH:16])([CH3:14])[CH3:13].C(N(CC)CC)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.C1(C)C=CC=CC=1>[Cl:10][C:5]1[CH:4]=[CH:3][C:2]([C:16]#[C:15][Si:12]([CH3:14])([CH3:13])[CH3:11])=[CH:7][C:6]=1[O:8][CH3:9]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 27695675-Bromo-2-chloroanisole

Product 1

HCID 198003224-Chloro-3-methoxyphenylethynyl-trimethylsilane

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

Commercially available 5-bromo-2-chloroanisole (1.0 g, 4.52 mmol), trimethylsilylacetylene (1.07 mL, 7.5 mmol) and triethylamine (15 mL) were added to anhydrous toluene (15 mL) and degassed by purging with nitrogen. Bis(acetato)bis(triphenylphosphine)palladium II (340 mg, 0.45 mmol) was added and the reaction mixture was heated to ˜95° C. for 30 min. The reaction mixture was cooled to room temperature, filtered to remove the catalyst, and diluted with ethyl acetate (150 mL). The organic layer was washed with saturated sodium bicarbonate (50 mL) and brine (50 mL) separated, dried over magnesium sulfate, filtered and concentrated. The residue was purified by flash column chromatography over silica gel eluted with hexane/ethyl acetate 20:1 to yield A60.1 (807 mg, 75%). 1H NMR (400 MHz): δ 7.40-7.25 (m, 2H), 7.10-7.00 (m, 1H), 3.90, (s, 3H), 0.24 (s, 9H).

Workup

  1. customdegassed
  2. customby purging with nitrogen
  3. temperatureThe reaction mixture was cooled to room temperature
  4. filtrationfiltered
  5. customto remove the catalyst
  6. additiondiluted with ethyl acetate (150 mL)
  7. washThe organic layer was washed with saturated sodium bicarbonate (50 mL) and brine (50 mL)
  8. customseparated
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe residue was purified by flash column chromatography over silica gel
  13. washeluted with hexane/ethyl acetate 20:1
  14. customto yield A60.1 (807 mg, 75%)

Sources & evidence

ORD record
ord-375a91a8cea641628cc76ec82565a953
Source dataset
uspto-grants-2010_06
Patent number
US07737279B2

Reaction notes

Loading…