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

HRID 489734Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 489734
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]

Komponenten

7

Edukt 3

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

Produkt 1

HCID 222629181H-Pyrrolo[2,3-b]pyridine-3-acetonitrile, 1-(methylsulfonyl)-Ausbeute 81,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 313Hydrochloric AcidLösungsmittelHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-80a8f1a05ee84d5bb60db16d6416280c
Quelldatensatz
uspto-grants-2005_12
Patentnummer
US06979696B2

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