Sodium hydride → HCID 86672285, Verbindung

HRID 2359814Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2359814
[H-].[Na+].[C:3]([O:7][C:8]([NH:10][C:11]1[N:16]=[C:15]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH:14]=[CH:13][CH:12]=1)=[O:9])([CH3:6])([CH3:5])[CH3:4].Br[CH2:23][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25].[Cl-].[NH4+]>CN(C)C=O.O>[C:27]([O:26][C:24](=[O:25])[CH2:23][N:10]([C:8]([O:7][C:3]([CH3:6])([CH3:5])[CH3:4])=[O:9])[C:11]1[CH:12]=[CH:13][CH:14]=[C:15]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[N:16]=1)([CH3:30])([CH3:29])[CH3:28]

Komponenten

7

Edukt 4

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 79177tert-Butyl bromoacetateHCID 19349079Ethyl 6-[(tert-butoxycarbonyl)amino]pyridine-2-carboxylate

Produkt 1

HCID 86672285HCID 86672285, VerbindungAusbeute 93,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel2×

Versuchsvorschrift

To a solution of sodium hydride (mineral oil 55% dispersion) (15.7 g, 0.360 mol) in N,N-dimethylformamide (362 ml) was added dropwise a solution of ethyl 6-tert-butoxycarbonylaminopyridin-2-carboxylate (see WO 2006/074884A) (81.2 g, 0.305 mol) in N,N-dimethylformamide (300 ml) over 20 minutes under ice cooling in an argon atmosphere, followed by stirring at room temperature for 1 hour. tert-Butyl bromoacetate (54.0 ml, 0.366 mol) was then added dropwise over 10 minutes under ice cooling, followed by further stirring at room temperature for 1 hour. After completion of the reaction, to the reaction solution was added an aqueous solution in which ammonium chloride (1.77 g, 33.0 mmol) was dissolved in water (300 ml), followed by extraction with toluene. The separated organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography (eluent; hexane:ethyl acetate=9:1→4:1 (V/V)), and fractions containing the desired compound were concentrated under reduced pressure to afford the title compound (108 g) as a pale yellow liquid. (Yield: 93%)

Aufarbeitung

  1. stirringby further stirring at room temperature for 1 hour
  2. customAfter completion of the reaction
  3. extractionfollowed by extraction with toluene
  4. washThe separated organic layer was washed with a saturated aqueous sodium chloride solution
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. additioncontaining the desired compound
  8. concentrationwere concentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-bd7bdf254f1347b68bb33f5d65165fc0
Quelldatensatz
uspto-grants-2014_04
Patentnummer
US08685986B2

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