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

HRID 963432노트

반응식

HRID 963432 반응식
[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]

참가 물질

9

반응물 4

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

생성물 1

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

시약·촉매·용매 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 887Methanol용매HCID 6228Dimethylformamide용매

실험 절차

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°.

후처리

  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

출처 및 근거

ORD 기록
ord-0b11cb7be4414163baec91f68e5235e8
출처 데이터셋
uspto-grants-1998_06
특허 번호
US05763450

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