Reaktion #448496

ord-8f97c3f1864e40b4ab223bbc3ce56383

Reaktionsgleichung

C#CC[C@@H]1C[C@H]2[C@@H]3CCC(=O)[C@@]3(C)CC[C@@H]2[C@@]2(C)CCC(=O)C[C@]12O
6β-Propargyl-5α-hydroxyandrostane-3,17-dione
C[C@]12CC[C@H]3[C@@H](CC[C@@]4(O)CCCC[C@]34C)[C@@H]1CC13OCCOC12OCCO3
6β-propargyl bisketal
C[C@]12CC[C@H]3[C@@H](CC[C@@]4(O)CCCC[C@]34C)[C@@H]1CC13OCCOC12OCCO3
17,17-bis(ethylenedioxy)androstane-5α-ol
[Br-].[K+]
KBr
→
C#CC[C@@H]1C[C@@H]2[C@H](CC[C@]3(C)C(=O)CC[C@@H]23)[C@@]2(C)CCC(=O)C=C12
6β-Propargyl-4-androstene-3,17-dione
Ausbeute 90.0%

Edukte

C#CC[C@@H]1C[C@H]2[C@@H]3CCC(=O)[C@@]3(C)CC[C@@H]2[C@@]2(C)CCC(=O)C[C@]12O
6β-Propargyl-5α-hydroxyandrostane-3,17-dione
C[C@]12CC[C@H]3[C@@H](CC[C@@]4(O)CCCC[C@]34C)[C@@H]1CC13OCCOC12OCCO3
6β-propargyl bisketal
C[C@]12CC[C@H]3[C@@H](CC[C@@]4(O)CCCC[C@]34C)[C@@H]1CC13OCCOC12OCCO3
17,17-bis(ethylenedioxy)androstane-5α-ol
[Br-].[K+]
KBr

Reagenzien

Keine

Lösungsmittel

CCOC(C)=O
ethyl acetate
CC(C)=O
acetone

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    workup.ADDITIONp-TSOH (5 mg) was added
  2. 2
    Waschenwashed (5% NaHCO3, brine, water)
  3. 3
    Sonstigedried
  4. 4
    SonstigeThe ethyl acetate was removed in vacuo
  5. 5
    Sonstigethe product was purified by column chromatography
  6. 6
    Sonstigeto yield the dione 90% yield

Vorschrift

6β-Propargyl-5α-hydroxyandrostane-3,17-dione (10). The 6β-propargyl bisketal 8 (0.6 mmol) was dissolved in acetone (30 ml) and p-TSOH (5 mg) was added. The reaction mixture was stirred at room temperature for 3 hours, diluted with ethyl acetate, washed (5% NaHCO3, brine, water) and dried. The ethyl acetate was removed in vacuo and the product was purified by column chromatography to yield the dione 90% yield; m.p. 145°-146° C.; IR (KBr) 3475 (C C--H), 3300 (OH), 2100, 1735 and 1715 (C=O) cm-1 ; 1H-NMR (CDCl3) δ 0.91 (s, 3H, 18-CH3), 1.21 (s, 3H 19-CH3), 3.0 (d, 1H, 4β-H).

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US05866558uspto-grants-1999_02