Toluene → Ethyl 3-(6-methylpyridin-2-yl)-3-oxopropanoate

HRID 751254

Reaktionsgleichung

Reaktionsgleichung von HRID 751254
[O-]CC.[Na+].C1(C)C=CC=CC=1.[C:12]([O:15][CH2:16][CH3:17])(=[O:14])[CH3:13].C[O:19][C:20]([C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH3:28])[N:23]=1)=O>C(O)(=O)C>[CH2:16]([O:15][C:12](=[O:14])[CH2:13][C:20]([C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH3:28])[N:23]=1)=[O:19])[CH3:17]

Komponenten

6

Edukt 4

HCID 1140TolueneHCID 8857Ethyl AcetateHCID 73022Methyl 6-methylpyridine-2-carboxylateHCID 2723922Sodium ethoxide

Produkt 1

HCID 59710028Ethyl 3-(6-methylpyridin-2-yl)-3-oxopropanoateAusbeute 112,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Reaktionsbedingungen

Temperatur
92 °C

Versuchsvorschrift

Stir a mixture of sodium ethoxide (90 g, 1.32 mol, 2 eq), toluene (0.5 L, 5 vol), and ethyl acetate (0.2 L, 1.98 mol, 3 eq) in a 2 L flask equipped with reflux condenser, mechanical stirrer, and nitrogen inlet. After 1 h, add 6-methyl-pyridine-2-carboxylic acid methyl ester (Cheung, Y, Tetrahedron Lett. 1979, 40, 3809-10; 100 g, 0.66 mol). Heat the mixture at reflux (92° C.) for 20 h. Cool the mixture to room temperature and acidify with glacial acetic acid to pH 6. Wash the resulting gel with water (0.5 L). Separate the layers and extract the aqueous layer with toluene (1×0.5 L) Dry the combined organic layers (sodium sulfate), filter, and concentrate in vacuo to yield the subtitled product (154 g) as a dark oil in 86% purity by HPLC analysis. MS ES+ m/e 208 (M+1).

Aufarbeitung

  1. customequipped
  2. temperaturewith reflux condenser, mechanical stirrer, and nitrogen inlet
  3. temperatureHeat the mixture
  4. temperatureCool the mixture to room temperature
  5. washWash the resulting gel with water (0.5 L)
  6. customSeparate the layers
  7. extractionextract the aqueous layer with toluene (1×0.5 L)
  8. dry with materialDry the combined organic layers (sodium sulfate)
  9. filtrationfilter
  10. concentrationconcentrate in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-9e7952648ad74ddc88db4efa9ed90fb9
Quelldatensatz
uspto-grants-2008_07
Patentnummer
US07405299B2

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