Triethylamine → 5-[(2-Fluorophenyl)ethynyl]-4-methyl-1,3-thiazole

HRID 967744노트

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HRID 967744 반응식
Br[C:2]1[S:6][CH:5]=[N:4][C:3]=1[CH3:7].C(N(CC)CC)C.[F:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[C:22]#[CH:23]>COCCOC.C(OCC)(=O)C.[Cu]I.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>[F:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[C:22]#[C:23][C:2]1[S:6][CH:5]=[N:4][C:3]=1[CH3:7]

참가 물질

8

반응물 3

HCID 8471TriethylamineHCID 6433581-Ethynyl-2-fluorobenzeneHCID 150209975-Bromo-4-methyl-1,3-thiazole

생성물 1

HCID 222913245-[(2-Fluorophenyl)ethynyl]-4-methyl-1,3-thiazole수율 113.4%

시약·촉매·용매 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 80711,2-Dimethoxyethane용매HCID 8857Ethyl Acetate용매2회

실험 절차

5-Bromo-4-methyl-1,3-thiazole (500 mg, 2.8 mmol) and CuI (120 mg, 0.63 mmol) were combined in DME (5 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (2.0 mL, 14 mmol) and PdCl2(PPh3)2 (220 mg, 0.32 mmol) were added, followed by the dropwise addition of (2-fluorophenyl)acetylene (1.0 g, 8.3 mmol). The reaction mixture was heated and after 3 h at reflux, allowed to cool, diluted with ethyl acetate (20 mL), and filtered through Celite™. The filter pad was washed thoroughly with ethyl acetate and the combined filtrates were washed with water (20 mL), brine (20 mL), dried over Na2SO4, and filtered. The filtrate was concentrated in vacuo, and the residue was purified by column chromatography on silica gel eluting with 95:5 hexane:ethyl acetate to afford 5-[(2-fluorophenyl)ethynyl]-4-methyl-1,3-thiazole (690 mg, 56% yield) as a red oil. 1H NMR (CDCl3, 300 MHz) δ 8.65 (s, 1H), 7.53–7.47 (m, 1H), 7.36–7.26 (m, 1H), 7.17–7.09 (m, 2H), 2.62 (s, 3H). MS (ESI) 217.3 (M+).

후처리

  1. customargon gas was bubbled through the suspension for several minutes
  2. customto deoxygenate the mixture
  3. temperatureThe reaction mixture was heated and after 3 h
  4. temperatureat reflux
  5. temperatureto cool
  6. filtrationfiltered through Celite™
  7. washThe filter pad was washed thoroughly with ethyl acetate
  8. washthe combined filtrates were washed with water (20 mL), brine (20 mL)
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated in vacuo
  12. customthe residue was purified by column chromatography on silica gel eluting with 95:5 hexane

출처 및 근거

ORD 기록
ord-e0ffbac1885542e98f2b6907707ff54c
출처 데이터셋
uspto-grants-2005_10
특허 번호
US06956049B1

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