Carbon Dioxide → Methyl 11-methoxy-6,11-dihydrodibenz[b,e]oxepin-3-carboxylate

HRID 892494

Reaktionsgleichung

Reaktionsgleichung von HRID 892494
Br[C:2]1[CH:3]=[CH:4][C:5]2[CH:11]([O:12][CH3:13])[C:10]3[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=3[CH2:8][O:7][C:6]=2[CH:18]=1.C([Li])CCC.[CH3:24]CCCCC.[C:30](=[O:32])=[O:31].S(=O)(=O)(O)O>O1CCCC1.CO>[CH3:13][O:12][CH:11]1[C:10]2[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=2[CH2:8][O:7][C:6]2[CH:18]=[C:2]([C:30]([O:32][CH3:24])=[O:31])[CH:3]=[CH:4][C:5]1=2

Komponenten

7

Edukt 4

HCID 280Carbon DioxideHCID 1118Sulfuric AcidHCID 150931363-Bromo-11-methoxy-6,11-dihydrodibenz[b,e]oxepineHCID 178418244HCID 178418244, Verbindung

Produkt 1

HCID 9994021Methyl 11-methoxy-6,11-dihydrodibenz[b,e]oxepin-3-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 887MethanolLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

3-Bromo-11-methoxy-6,11-dihydrodibenz[b,e]oxepine, 30 g, was dissolved in 500 ml of tetrahydrofuran. After cooling to -78° C., 65 ml of 1.6 N n-butyl lithium/hexane solution was dropwise added to the solution in a nitrogen atmosphere followed by stirring at -78° C. for further 40 minutes. The reaction solution was dropwise added onto 100 g of dry ice, which was allowed to stand to elevate to room temperature. The solvent was distilled off under reduced pressure. To the residue obtained, were added 500 ml of methanol and 10 ml of conc. sulfuric acid. The mixture was heated to reflux for 2 hours. After allowing to cool, the solvent was distilled off under reduced pressure. The residue was extracted with 500 ml of ethyl acetate. After washing successively with saturated sodium chloride aqueous solution, saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, the extract was dried over anhydrous magnesium sulfate. The solvent was then distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (eluting solvent; hexane:ethyl acetate=1:1) to give 19.3 g of the product as pale yellow oil.

Aufarbeitung

  1. customto elevate to room temperature
  2. distillationThe solvent was distilled off under reduced pressure
  3. customTo the residue obtained
  4. temperatureThe mixture was heated
  5. temperatureto reflux for 2 hours
  6. temperatureto cool
  7. distillationthe solvent was distilled off under reduced pressure
  8. extractionThe residue was extracted with 500 ml of ethyl acetate
  9. washAfter washing successively with saturated sodium chloride aqueous solution, saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution
  10. dry with materialthe extract was dried over anhydrous magnesium sulfate
  11. distillationThe solvent was then distilled off under reduced pressure
  12. washThe residue was subjected to silica gel column chromatography (eluting solvent; hexane:ethyl acetate=1:1)

Quellen und Nachweise

ORD-Eintrag
ord-1e9bdf312ad84b28ad7ca998db7f6bc9
Quelldatensatz
uspto-grants-1992_06
Patentnummer
US05118701

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