Reaktion #2075751

ord-7628d06328d143c08361ef07923c3693

Reaktionsgleichung

O=C([O-])[O-].[Na+].[Na+]
sodium carbonate
C=CCBr
allyl bromide
CC(=O)O[C@H]1[C@@H](N2CCCC2)C[C@H]2[C@@H]3CC[C@H]4C[C@H](O)[C@@H](N5CCOCC5)C[C@]4(C)[C@H]3CC[C@@]21C
2β-(4-morpholinyl)-16β-(1-pyrrolidinyl)-5α-androstan-3α,17β-diol 17-acetate
CC(=O)O[C@H]1[C@@H](N2CCCC2)C[C@H]2[C@@H]3CC[C@H]4C[C@H](O)[C@@H](N5CCOCC5)C[C@]4(C)[C@H]3CC[C@@]21C
Compound VIII
CC(=O)O[C@H]1[C@@H](N2CCCC2)C[C@H]2[C@@H]3CC[C@H]4C[C@H](O)[C@@H](N5CCOCC5)C[C@]4(C)[C@H]3CC[C@@]21C
2β-(4-morpholinyl)-16β-(1-pyrrolidinyl)-5α-androstan-3α,17β-diol 17-acetate
→
C=CC[N+]1([C@H]2C[C@H]3[C@@H]4CC[C@H]5C[C@H](O)[C@@H](N6CCOCC6)C[C@]5(C)[C@H]4CC[C@]3(C)[C@H]2OC(C)=O)CCCC1.[Br-]
1-[17β-acetyloxy-3α-hydroxy-2β-(4-morpholinyl)-5α-androstan-16β-yl]-1-(2-propenyl)pyrrolidinium bromide

Edukte

O=C([O-])[O-].[Na+].[Na+]
sodium carbonate
C=CCBr
allyl bromide
CC(=O)O[C@H]1[C@@H](N2CCCC2)C[C@H]2[C@@H]3CC[C@H]4C[C@H](O)[C@@H](N5CCOCC5)C[C@]4(C)[C@H]3CC[C@@]21C
2β-(4-morpholinyl)-16β-(1-pyrrolidinyl)-5α-androstan-3α,17β-diol 17-acetate
CC(=O)O[C@H]1[C@@H](N2CCCC2)C[C@H]2[C@@H]3CC[C@H]4C[C@H](O)[C@@H](N5CCOCC5)C[C@]4(C)[C@H]3CC[C@@]21C
Compound VIII
CC(=O)O[C@H]1[C@@H](N2CCCC2)C[C@H]2[C@@H]3CC[C@H]4C[C@H](O)[C@@H](N5CCOCC5)C[C@]4(C)[C@H]3CC[C@@]21C
2β-(4-morpholinyl)-16β-(1-pyrrolidinyl)-5α-androstan-3α,17β-diol 17-acetate

Reagenzien

Keine

Lösungsmittel

ClCCl
dichloromethane
ClCCl
dichloromethane

Reaktionsbedingungen

Temperatur
22.5°CELSIUS
Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    SonstigeIn a three neck flask equipped
  2. 2
    Temperaturwith heated mantle
  3. 3
    workup.STIRRINGThe resulting mixture was stirred during 5-10 min
  4. 4
    workup.STIRRINGThe resulting solution was stirred
  5. 5
    Temperaturunder reflux for 22 hours
  6. 6
    Filtrationfiltered (membrane 0.45 microns) under nitrogen atmosphere
  7. 7
    SonstigeThe solvent was removed under vacuum
  8. 8
    Sonstigethe temperature below 20° C
  9. 9
    SonstigeThe foam obtained
  10. 10
    Einengenconcentrated under vacuum
  11. 11
    Sonstigethe temperature below 20° C.
  12. 12
    workup.DISSOLUTIONOnce again the residue was dissolved at room temperature under nitrogen atmosphere in dichloromethane (22 mL)

Vorschrift

In a three neck flask equipped with heated mantle, thermometer and magnetic stirrer, was charged dichloromethane (20 mL), sodium carbonate (2.0 g, 0.081 mol) and slowly allyl bromide (0.692 mL, 0.00818 mol) at 20-22° C. under N2 atmosphere. The mixture was stirred during 5 min and 2β-(4-morpholinyl)-16β-(1-pyrrolidinyl)-5α-androstan-3α,17β-diol 17-acetate (Compound VIII) (2.0 g, 4.09×10−3 mol) was added. The resulting mixture was stirred during 5-10 min. The resulting solution was stirred under reflux for 22 hours. The mixture was then cooled to room temperature (20-25° C.) and filtered (membrane 0.45 microns) under nitrogen atmosphere. The solvent was removed under vacuum keeping the temperature below 20° C. The foam obtained was dissolved with dichloromethane (10 mL) and concentrated under vacuum keeping the temperature below 20° C.; this procedure was repeated twice. Once again the residue was dissolved at room temperature under nitrogen atmosphere in dichloromethane (22 mL).

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US07642246B2uspto-grants-2010_01