Ethyl acetamidocyanoacetate → Ethyl (acetylamino)(bicyclo[4.2.0]octa-1,3,5-trien-7-yl)cyanoacetate

HRID 74765

Reaktionsgleichung

Reaktionsgleichung von HRID 74765
[Na].[C:2]([NH:5][CH:6]([C:12]#[N:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:4])[CH3:3].Br[CH:15]1[CH2:22][C:21]2[C:16]1=[CH:17][CH:18]=[CH:19][CH:20]=2>C(O)C>[C:2]([NH:5][C:6]([CH:15]1[CH2:22][C:21]2[C:16]1=[CH:17][CH:18]=[CH:19][CH:20]=2)([C:12]#[N:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:4])[CH3:3]

Komponenten

5

Edukt 3

HCID 95422Ethyl acetamidocyanoacetateHCID 5685917-Bromobicyclo[4.2.0]octa-1,3,5-trieneHCID 5360545Sodium

Produkt 1

HCID 86685739Ethyl (acetylamino)(bicyclo[4.2.0]octa-1,3,5-trien-7-yl)cyanoacetateAusbeute 95,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Versuchsvorschrift

Sodium (464 mg, 20.2 mmol, 1.2 eq.) was allowed to react with absolute ethanol (40 mL, 0.42 M); to the resulting mixture was added ethyl 2-(acetylamino)-2-cyanoacetate (3.44 g, 20.2 mmol, 1.2 eq.). After 20 minutes at 60° C., 7-bromobicyclo[4.2.0]octa-1,3,5-triene (3.092 g, 16.89 mmol, 1 eq.) was added and the reaction mixture was heated at reflux overnight, then filtered and concentrated in vacuo. The residue was diluted with water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a dark oil, which was purified by silica gel chromatography (Gradient: 0% to 50% ethyl acetate in heptane) to give #99 (4.38 g) as a yellow gum. LC-MS: m/z 273.2 [M+H+], retention time=2.36 minutes.

Aufarbeitung

  1. temperaturethe reaction mixture was heated
  2. temperatureat reflux overnight
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. additionThe residue was diluted with water
  6. extractionextracted with ethyl acetate
  7. washThe organic layer was washed with brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customto give a dark oil, which
  12. customwas purified by silica gel chromatography (Gradient: 0% to 50% ethyl acetate in heptane)

Quellen und Nachweise

ORD-Eintrag
ord-1049b729081445a9a898331059c3b8f8
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08828401B2

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