Reaktion #554635

ord-5596620960c34ab1b1f43852351e4fcd

Reaktionsgleichung

COc1ccc2c(c1)CC[C@@H]1[C@@H]2CC[C@]2(C)[C@@H](O)C=C[C@@H]12
3-methoxy-17β-hydroxyestra-1,3,5(10),15-tetraene
c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
O=C(O)c1ccc([N+](=O)[O-])cc1
4-nitrobenzoic acid
CC(C)OC(=O)N=NC(=O)OC(C)C
diisopropyl azodicarboxylate
[Cl-].[Na+]
sodium chloride
→
COc1ccc2c(c1)CC[C@@H]1[C@@H]2CC[C@]2(C)C(OC(=O)c3ccc([N+](=O)[O-])cc3)C=C[C@@H]12
title compound
Ausbeute 78.5%
COc1ccc2c(c1)CC[C@@H]1[C@@H]2CC[C@]2(C)C(OC(=O)c3ccc([N+](=O)[O-])cc3)C=C[C@@H]12
3-Methoxy-estra-1,3,5(10),15-tetraen-17-yl 4-nitrobenzoate
Ausbeute 78.5%

Edukte

COc1ccc2c(c1)CC[C@@H]1[C@@H]2CC[C@]2(C)[C@@H](O)C=C[C@@H]12
3-methoxy-17β-hydroxyestra-1,3,5(10),15-tetraene
c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
O=C(O)c1ccc([N+](=O)[O-])cc1
4-nitrobenzoic acid
CC(C)OC(=O)N=NC(=O)OC(C)C
diisopropyl azodicarboxylate
[Cl-].[Na+]
sodium chloride

Reagenzien

Keine

Lösungsmittel

C1CCOC1
tetrahydrofuran

Reaktionsbedingungen

Temperatur
23°CELSIUS
Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Extraktionextracted with ethyl acetate
  2. 2
    Waschenthe combined organic extracts are washed with saturated sodium chloride solution
  3. 3
    Trocknendried over sodium sulfate
  4. 4
    SonstigeThe residue obtained
  5. 5
    Filtrationafter filtration and solvent removal
  6. 6
    workup.ADDITIONtreated with 80 ml of a 30% hydrogen peroxide solution
  7. 7
    Temperaturwith cooling
  8. 8
    workup.ADDITIONafter 20 minutes poured
  9. 9
    Temperaturwith cooling into 600 ml of a semi-concentrated sodium thiosulfate solution
  10. 10
    ExtraktionThis is extracted with ethyl acetate
  11. 11
    Waschenthe combined organic extracts are washed with saturated sodium chloride solution
  12. 12
    Trocknendried over sodium sulfate
  13. 13
    SonstigeThe residue obtained
  14. 14
    Filtrationafter filtration and solvent removal
  15. 15
    Sonstigeis purified by recrystallisation

Vorschrift

The solution of 43.9 g of 3-methoxy-17β-hydroxyestra-1,3,5(10),15-tetraene in 1.61 tetrahydrofuran is treated with 121 g of triphenylphosphine, 27.1 g of 4-nitrobenzoic acid and 30.9 ml of diisopropyl azodicarboxylate and stirred at 23° C. for 2 hours. This is treated with saturated sodium chloride solution, extracted with ethyl acetate, and the combined organic extracts are washed with saturated sodium chloride solution and dried over sodium sulfate. The residue obtained after filtration and solvent removal is taken up 1.2 l acetone, treated with 80 ml of a 30% hydrogen peroxide solution with cooling, and after 20 minutes poured with cooling into 600 ml of a semi-concentrated sodium thiosulfate solution. This is extracted with ethyl acetate, and the combined organic extracts are washed with saturated sodium chloride solution and dried over sodium sulfate. The residue obtained after filtration and solvent removal is purified by recrystallisation. 52.5 g of the title compound are isolated.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08623850B2uspto-grants-2014_01