Ethanol → 4-Aminopyrazolo[1,5-a]pyridine-2-carboxylic acid ethyl ester

HRID 2039784Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2039784
OS(O)(=O)=O.[NH2:6][C:7]1[C:8]2[N:9]([N:13]=[C:14]([C:16]([OH:18])=[O:17])[CH:15]=2)[CH:10]=[CH:11][CH:12]=1.C([O-])(O)=O.[Na+].[CH2:24](O)[CH3:25]>>[CH2:24]([O:17][C:16]([C:14]1[CH:15]=[C:8]2[C:7]([NH2:6])=[CH:12][CH:11]=[CH:10][N:9]2[N:13]=1)=[O:18])[CH3:25]

Komponenten

5

Edukt 4

HCID 702EthanolHCID 1118Sulfuric AcidHCID 516892Sodium BicarbonateHCID 686499974-Aminopyrazolo[1,5-a]pyridine-2-carboxylic acid

Produkt 1

HCID 595390024-Aminopyrazolo[1,5-a]pyridine-2-carboxylic acid ethyl ester

Reaktionsbedingungen

Temperatur
75 °C

Versuchsvorschrift

50% Aqueous H2SO4 (60 mL) is added to 4-Aminopyrazolo[1,5-a]pyridine-2,3-dicarboxylic acid dimethyl ester (1.47 g, 5.90 mmol) under air. The mixture is warmed to 80° C. After 6.5 h, the solution is cooled to 0° C. and then neutralized with 10 N aq. NaOH. The resulting slurry is acidified to pH 3 with 1 M aq. HCl. The volatiles are removed under reduced pressure. The residue is washed with 30% EtOH in CH2Cl2. The volatiles are removed under reduced pressure to afford 4-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid in Na2SO4. LC-MS m/z (M+H+): 178.01. A solution of conc. H2SO4 (6.0 mL) and ethanol (120 mL) is added to the crude 4-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid. The mixture is warmed to 75° C. for 3.5 h. After cooling to rt, the mixture is made basic with dropwise addition of sat. aq. NaHCO3. The volatiles are removed under reduced pressure. The aqueous mixture is filtered (EtOAc rinse). The aqueous solution is extracted with EtOAc (3×250 mL). The combined organics are dried over Na2SO4, filtered, and concentrated to afford the title compound as dark brown solid. LC-MS m/z (M+Na+): 228.03.

Aufarbeitung

  1. temperatureAfter cooling to rt
  2. customThe volatiles are removed under reduced pressure
  3. filtrationThe aqueous mixture is filtered
  4. wash(EtOAc rinse)
  5. extractionThe aqueous solution is extracted with EtOAc (3×250 mL)
  6. dry with materialThe combined organics are dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-8c412eeef1224bbbaefdcb862b6eba94
Quelldatensatz
uspto-grants-2013_11
Patentnummer
US08580812B2

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