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

HRID 489734노트

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HRID 489734 반응식
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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 313Hydrochloric Acid용매HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

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온도
0 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-80a8f1a05ee84d5bb60db16d6416280c
출처 데이터셋
uspto-grants-2005_12
특허 번호
US06979696B2

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