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

HRID 41595

反応式

HRID 41595 の反応式
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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 1140Toluene溶媒

反応条件

温度
120 °C

実験手順

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)].

後処理

  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)

出典と根拠

ORDレコード
ord-ba31f049f5f24f55a3d18e92a376ae81
出典データセット
uspto-grants-2013_09
特許番号
US08530648B2

関連ノート

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