1,4-Dioxane → Ethyl 3,5-diethylpyridine-4-carboxylate

HRID 630148ノート

反応式

HRID 630148 の反応式
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6](Br)[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].[CH2:14]([Zn]CC)[CH3:15].O1CCO[CH2:21][CH2:20]1>>[CH2:14]([C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH2:20][CH3:21])[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH3:15]

参加物

4

反応物 3

HCID 312751,4-DioxaneHCID 46311332Ethyl 3,5-dibromoisonicotinateHCID 178418750HCID 178418750、化合物

生成物 1

HCID 59589455Ethyl 3,5-diethylpyridine-4-carboxylate収率 54.8%

反応条件

温度
70 °C

実験手順

To a solution of ethyl 3,5-dibromopyridine-4-carboxylate (5.98 g, 19.35 mmol) in anhydrous dioxane (40 mL) was added at room temperature (1,1′-bis(diphenylphosphino)ferrocene)dichloropalladium (II) (424 mg, 0.580 mmol). Diethylzinc (3.58 g, 23.8 mL, 28.95 mmol, 15% solution in toluene) was then added dropwise. The reaction mixture was heated at 70° C. for 45 minutes, then cooled to room temperature and quenched with MeOH. The resulting mixture was extracted with ethyl acetate (2×100 mL), washed with water, 0.1 N HCl, and brine. The organic layer was dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated, and the residue was purified by CombiFlash using 0-30% ethyl acetate in hexane to provide ethyl 3,5-diethylpyridine-4-carboxylate as a pale yellow oil (2.2 g, 54.8% yield); 1H NMR (400 MHz, CDCl3): δ 1.23 (t, 6H), 1.40 (t, 3H), 2.64 (q, 4H), 4.44 (q, 2H), 8.36 (s, 2H), M+208.5; M+180.2.

後処理

  1. temperaturecooled to room temperature
  2. customquenched with MeOH
  3. extractionThe resulting mixture was extracted with ethyl acetate (2×100 mL)
  4. washwashed with water, 0.1 N HCl, and brine
  5. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customThe filtrate was evaporated
  8. customthe residue was purified by CombiFlash

出典と根拠

ORDレコード
ord-48dff454431a402fa6171bebff39630d
出典データセット
uspto-grants-2016_04
特許番号
US09315521B2

反応ノート

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