Pyrazole → 2-methyl-4-(1H-pyrazol-1-yl)pyridine

HRID 41595

반응식

HRID 41595 반응식
Br[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([CH3:8])[CH:3]=1.[NH:9]1[CH:13]=[CH:12][CH:11]=[N:10]1.N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.C([O-])([O-])=O.[K+].[K+]>C1(C)C=CC=CC=1.[Cu]I>[CH3:8][C:4]1[CH:3]=[C:2]([N:9]2[CH:13]=[CH:12][CH:11]=[N:10]2)[CH:7]=[CH:6][N:5]=1

참가 물질

7

반응물 4

HCID 1048PyrazoleHCID 13181,10-PhenanthrolineHCID 11430Potassium CarbonateHCID 27628354-Bromo-2-methylpyridine

생성물 1

HCID 672531852-methyl-4-(1H-pyrazol-1-yl)pyridine수율 92%

시약·촉매·용매 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 1140Toluene용매

반응 조건

온도
120 °C

실험 절차

To a mixture of 4-bromo-2-methylpyridine [22282-99-1] (350 mg, 2.05 mmol), 1H-pyrazole (140 mg, 2.05 mmol), 1,10-phenanthroline (74 mg, 0.41 mmol) and K2CO3 (567 mg, 4.1 mmol) in toluene (2 mL), CuI (19 mg, 0.1 mmol) was added and the reaction mixture was heated at 120° C. for 70 h in a sealed tube. The reaction mixture was cooled to rt, quenched with water (50 mL) and extracted with dichloromethane (150 mL). The organic layer was washed with brine and dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude product was purified flash column chromatography (eluent: 30% ethyl acetate in hexane) to yield the title compound (300 mg, 92%). [1H NMR (300 MHz, CDCl3) ♀ ppm 8.53 (d, 1H), 8.02 (d, 1H), 7.77 (d, 1H), 7.55 (d, 1H), 7.44-7.40 (m, 1H), 6.52 (t, 1H), 2.62 (s, 3H); TLC Rf=0.28 (ethyl acetate/hexane 30:70)].

후처리

  1. additionwas added
  2. temperatureThe reaction mixture was cooled to rt
  3. customquenched with water (50 mL)
  4. extractionextracted with dichloromethane (150 mL)
  5. washThe organic layer was washed with brine
  6. dry with materialdried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe crude product was purified flash column chromatography (eluent: 30% ethyl acetate in hexane)

출처 및 근거

ORD 기록
ord-ba31f049f5f24f55a3d18e92a376ae81
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08530648B2

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