Diethyl Carbonate → Ethyl 2-(pyridazin-3-yl)acetate

HRID 931172ノート

反応式

HRID 931172 の反応式
C([N-]C(C)C)(C)C.[Li+].[CH3:9][C:10]1[N:11]=[N:12][CH:13]=[CH:14][CH:15]=1.[C:16](=O)([O:20]CC)[O:17][CH2:18][CH3:19]>O1CCCC1>[N:12]1[CH:13]=[CH:14][CH:15]=[C:10]([CH2:9][C:16]([O:17][CH2:18][CH3:19])=[O:20])[N:11]=1

参加物

5

反応物 3

HCID 7766Diethyl CarbonateHCID 742083-MethylpyridazineHCID 2724682Lithium diisopropylamide

生成物 1

HCID 52911166Ethyl 2-(pyridazin-3-yl)acetate収率 6.8%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

Lithium diisopropylamide (2M in tetrahydrofuran, 6.83 g, 63.7 mmol) was added dropwise to a stirred solution of 3-methylpyridazine (5.0 g, 53.12 mmol) in anhydrous tetrahydrofuran (80 mL) at −78° C. under a nitrogen atmosphere over a period of 20 min. The mixture was allowed to warm to room temperature. The mixture was stirred for 1 h at room temperature and cooled again to −78° C. Diethyl carbonate (12.57 g, 106.2 mmol) in anhydrous tetrahydrofuran (20 mL) was added at −78° C. over a period of 20 min. The reaction mixture was allowed to warm to room temperature, stirred for 16 h and partitioned between ethyl acetate and a saturated aqueous solution of ammonium chloride. The organics were dried over sodium sulfate and concentrated under reduced pressure. The resulting crude material was purified via column chromatography (100-200 mesh silica gel, 50-80% ethyl acetate in petroleum ether) to afford ethyl 2-(pyridazin-3-yl)acetate (600 mg). MS (ES+) (M+H) 167.1569.

後処理

  1. temperaturecooled again to −78° C
  2. temperatureto warm to room temperature
  3. stirringstirred for 16 h
  4. custompartitioned between ethyl acetate
  5. dry with materialThe organics were dried over sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe resulting crude material was purified via column chromatography (100-200 mesh silica gel, 50-80% ethyl acetate in petroleum ether)

出典と根拠

ORDレコード
ord-27d0977e32b84cbea03cf48cb871e3dd
出典データセット
uspto-grants-2016_03
特許番号
US09296745B2

反応ノート

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