p-Bromoacetophenone → 1-(4-Ethynylphenyl)ethan-1-one

HRID 963432

Reaktionsgleichung

Reaktionsgleichung von HRID 963432
[CH3:1][C:2]([C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][CH:5]=1)=[O:3].[C:11]([Si](C)(C)C)#[CH:12].C(N(CC)CC)C.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O.CO.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>[C:11]([C:7]1[CH:8]=[CH:9][C:4]([C:2](=[O:3])[CH3:1])=[CH:5][CH:6]=1)#[CH:12]

Komponenten

9

Edukt 4

HCID 7466p-BromoacetophenoneHCID 8471TriethylamineHCID 11430Potassium CarbonateHCID 66111Trimethylsilylacetylene

Produkt 1

HCID 51236261-(4-Ethynylphenyl)ethan-1-oneAusbeute 71 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 887MethanolLösungsmittelHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

2 g of 4-bromoacetophenone, 2.8 ml of ethynyltrimethylsilane, 140 mg of bis(triphenylphosphine)palladium dichloride, 3 ml of triethylamine and 14 mg of copper(I)iodide in 20 ml of N,N-dimethylformamide were stirred at 50° under argon for 2 hrs. After distillation of the solvent the residue was extracted once with 50 ml of ethyl acetate, once with 50 ml of 1N HCl and twice with 50 ml of water. The crude product was purified by silica gel chromatography in hexane/ethyl acetate 10:1 and distilled at 120°/0.1 Torr in a bulb-tube oven. 1.74 g (80%) were obtained as a colourless oil. This was dissolved in 17 ml of methanol, treated with 110 mg of potassium carbonate and stirred at room temperature for 1.5 hrs. After evaporation the product was extracted with 20 ml of ethyl acetate and 20 ml of water and then crystallized from 10 ml of hexane. 0.8 g (71%) of 1-(4-ethynyl-phenyl)-ethanone was obtained as white crystals. M.p. 71°.

Aufarbeitung

  1. distillationAfter distillation of the solvent the residue
  2. extractionwas extracted once with 50 ml of ethyl acetate, once with 50 ml of 1N HCl and twice with 50 ml of water
  3. customThe crude product was purified by silica gel chromatography in hexane/ethyl acetate 10:1
  4. distillationdistilled at 120°/0.1 Torr in a bulb-tube oven
  5. custom1.74 g (80%) were obtained as a colourless oil
  6. customAfter evaporation the product
  7. extractionwas extracted with 20 ml of ethyl acetate and 20 ml of water
  8. customcrystallized from 10 ml of hexane

Quellen und Nachweise

ORD-Eintrag
ord-0b11cb7be4414163baec91f68e5235e8
Quelldatensatz
uspto-grants-1998_06
Patentnummer
US05763450

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