Sulfuric Acid → Crotophorbolone

HRID 2410650

Reaktionsgleichung

Reaktionsgleichung von HRID 2410650
[CH3:1][C@H:2]1[C@:10]2([OH:24])[C@H:11]3[C@:16]([OH:22])([CH2:17][C:18]([CH2:20][OH:21])=[CH:19][C@H:9]2[C@@H:5]2[C:6]([CH3:8])([CH3:7])[C@:4]2([OH:25])[C@@H:3]1O)[C:14](=[O:15])[C:13]([CH3:23])=[CH:12]3.S(=O)(=O)(O)O>>[CH3:1][C@H:2]1[C@:10]2([OH:24])[CH:11]3[C@:16]([OH:22])([CH2:17][C:18]([CH2:20][OH:21])=[CH:19][C@H:9]2[C@H:5]([C:6]([CH3:8])=[CH2:7])[C:4](=[O:25])[CH2:3]1)[C:14](=[O:15])[C:13]([CH3:23])=[CH:12]3

Komponenten

3

Edukt 2

HCID 1118Sulfuric AcidHCID 442070Phorbol

Produkt 1

HCID 102259583CrotophorboloneAusbeute 39,2 %

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

To a 50 mL round-bottom flask containing a stirbar and phorbol (1.76 g, 4.82 mmol, 1.0 eq) at ambient temperature (23° C.) was added sulfuric acid (0.01 M aqueous H2SO4 solution: 16 mL, 0.3 M with respect to phorbol). The flask was equipped with a reflux condenser, the system flushed with a stream of dry nitrogen, and the cloudy, slightly yellow mixture heated to 90° C. After 1 h, the reaction vessel was cooled to room temperature (23° C.), the aqueous solution extracted with EtOAc, and the organic phase washed with brine. The organic phase was dried over Na2SO4, filtered, concentrated under reduced pressure, and purified by flash chromatography on a 4.5×18 cm silica gel column eluting with a solvent gradient from 75% to 90% EtOAc/petrol ether followed by elution with 100% EtOAc. The eluant was collected in 75 mL portions, and the crotophorbolone containing fractions were combined and concentrated to give crotophorbolone (654 mg).

Aufarbeitung

  1. customThe flask was equipped with a reflux condenser
  2. customthe system flushed with a stream of dry nitrogen
  3. temperaturethe reaction vessel was cooled to room temperature (23° C.)
  4. extractionthe aqueous solution extracted with EtOAc
  5. washthe organic phase washed with brine
  6. dry with materialThe organic phase was dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. custompurified by flash chromatography on a 4.5×18 cm silica gel column
  10. washeluting with a solvent gradient from 75% to 90% EtOAc/petrol ether
  11. washfollowed by elution with 100% EtOAc
  12. customThe eluant was collected in 75 mL portions
  13. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-e9888d26bdbe4aa0a53ebf628679228a
Quelldatensatz
uspto-grants-2014_08
Patentnummer
US08816122B2

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