Sodium hydride → 1H-Pyrrolo[2,3-b]pyridine-3-acetonitrile, 1-(methylsulfonyl)-

HRID 489734ノート

反応式

HRID 489734 の反応式
C(OP([CH2:9][C:10]#[N:11])(=O)OCC)C.[H-].[Na+].[CH3:14][S:15]([N:18]1[C:22]2=[N:23][CH:24]=[CH:25][CH:26]=[C:21]2[C:20](=O)[CH2:19]1)(=[O:17])=[O:16]>O1CCCC1.O.Cl>[CH3:14][S:15]([N:18]1[C:22]2=[N:23][CH:24]=[CH:25][CH:26]=[C:21]2[C:20]([CH2:9][C:10]#[N:11])=[CH:19]1)(=[O:16])=[O:17]

参加物

7

反応物 3

HCID 24758Sodium hydrideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 222629303H-Pyrrolo[2,3-b]pyridin-3-one, 1,2-dihydro-1-(methylsulfonyl)-

生成物 1

HCID 222629181H-Pyrrolo[2,3-b]pyridine-3-acetonitrile, 1-(methylsulfonyl)-収率 81.2%

試薬・触媒・溶媒 3

HCID 313Hydrochloric Acid溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

Diethyl(cyanomethyl)phosphonate (0.47 ml, 3.1 mmol) was dissolved in tetrahydrofuran (5 ml) and cooled to 0° C. Sodium hydride (0.12 g, 3.1 mmol) was added portionwise and the reaction was stirred for 10 min. 1-Methanesulfonyl-1,2-dihydro-pyrrolo[2,3-b]pyridin-3-one (0.332 g, 1.57 mmoles) suspended in tetrahydrofuran (3 ml) was added dropwise, whereupon it immediately dissolved. The reaction was stirred at room temperature for 2 h. The reaction mixture was diluted with water and neutralized with 1M hydrochloric acid The aqueous solution was extracted with ethyl acetate. The organic extract was washed with brine, dried (sodium sulfate) and concentrated under reduced pressure. The crude product was chromatographed over silica gel eluting with 50% ethyl acetate in hexane to provide pure (1-methanesulfonyl-1H-pyrrolo[2,3-b]pyridin-3-yl)-acetonitrile (0.30 g, 45%). 1H NMR (CDCl3) δ: 3.61 (3H, s), 3.81 (2H, s), 7.34 (1H, dd, J=4.8 Hz, 7.9 Hz), 8.02 (1H, dd, J=1.6 Hz, 7.9 Hz), 8.54 (1H, dd, J=1.6 Hz, 4.8 Hz).

後処理

  1. additionwas added dropwise, whereupon it
  2. dissolutionimmediately dissolved
  3. stirringThe reaction was stirred at room temperature for 2 h
  4. extractionwas extracted with ethyl acetate
  5. extractionThe organic extract
  6. washwas washed with brine
  7. dry with materialdried (sodium sulfate)
  8. concentrationconcentrated under reduced pressure
  9. customThe crude product was chromatographed over silica gel eluting with 50% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-80a8f1a05ee84d5bb60db16d6416280c
出典データセット
uspto-grants-2005_12
特許番号
US06979696B2

反応ノート

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