Reaktion #1693453

ord-d1cad07377974f45a498c629ece70bd0

Reaktionsgleichung

CC(=O)Oc1cc2c(c(OC(C)=O)c1)[C@H]1CC[C@]3(C)C(=O)CC[C@H]3[C@H]1CC2
rac.-1,3-diacetoxy-8α-estra-1,3,5(10)-trien-17-one
C=C(C)OC(C)=O
isopropenyl acetate
Cc1ccc(S(=O)(=O)O)cc1
p-toluenesulfonic acid
→
CC(=O)OC1=CC[C@H]2[C@H]3CCc4cc(OC(C)=O)cc(OC(C)=O)c4[C@H]3CC[C@]12C
rac.-1,3,17-triacetoxy-8α-estra-1,3,5(10),16-tetraene

Edukte

CC(=O)Oc1cc2c(c(OC(C)=O)c1)[C@H]1CC[C@]3(C)C(=O)CC[C@H]3[C@H]1CC2
rac.-1,3-diacetoxy-8α-estra-1,3,5(10)-trien-17-one
C=C(C)OC(C)=O
isopropenyl acetate
Cc1ccc(S(=O)(=O)O)cc1
p-toluenesulfonic acid

Reagenzien

Keine

Reaktionsbedingungen

Temperatur
125°CELSIUS
Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    workup.ADDITIONA mixture of 5 g
  2. 2
    workup.DISTILLATIONof isopropenyl acetate are gradually distilled off
  3. 3
    TemperaturAfter cooling
  4. 4
    workup.ADDITIONof pyridine is added
  5. 5
    workup.ADDITIONthe mixture is diluted with methylene chloride
  6. 6
    Waschenwashed with saturated sodium bicarbonate solution and water
  7. 7
    Trocknendried over sodium sulfate
  8. 8
    SonstigeThe solvent is evaporated under vacuum

Vorschrift

A mixture of 5 g. of rac.-1,3-diacetoxy-8α-estra-1,3,5(10)-trien-17-one, 100 ml. of isopropenyl acetate, and 14.4 g. of p-toluenesulfonic acid is heated for 21 hours under a slight N2 stream to 105° C. After the mixture has been heated to 125° C., 50 ml. of isopropenyl acetate are gradually distilled off. After cooling, 10 ml. of pyridine is added, the mixture is diluted with methylene chloride, washed with saturated sodium bicarbonate solution and water, and dried over sodium sulfate. The solvent is evaporated under vacuum. After chromatography on 260 g. of SiO2, 3 g. of oily rac.-1,3,17-triacetoxy-8α-estra-1,3,5(10),16-tetraene is obtained, which is further processed as the crude product.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US03951958uspto-grants-1976_04