Reaktion #93690

ord-88e04718e1d44870854fe8070f599930

Reaktionsgleichung

CC(C)(C)C(=O)O[C@H]1CC[C@]2(C)[C@H]3CC[C@]4(C)C(=O)[C@H]5C[C@H]5[C@H]4[C@@H]3[C@H](Cl)[C@H]3O[C@]32C1
7α-chloro-5,6β-epoxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one
→
CC(C)(C)C(=O)O[C@H]1CC[C@]2(C)[C@H]3CC[C@]4(C)C(=O)[C@H]5C[C@H]5[C@H]4[C@@H]3C=C[C@]2(O)C1
5-hydroxy-15β,16β-methylene-3β-pivaloyloxy-5β-androst-6-en-17-one
Ausbeute 74.6%

Edukte

CC(C)(C)C(=O)O[C@H]1CC[C@]2(C)[C@H]3CC[C@]4(C)C(=O)[C@H]5C[C@H]5[C@H]4[C@@H]3[C@H](Cl)[C@H]3O[C@]32C1
7α-chloro-5,6β-epoxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one

Reagenzien

[Zn]
zinc

Lösungsmittel

CC(=O)O
acetic acid
C1CCOC1
tetrahydrofuran

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    TemperaturAfter cooling
  2. 2
    Filtrationthe zinc is filtered off over "Celite"
  3. 3
    Waschenwashed with 5 l of methylene chloride
  4. 4
    workup.ADDITIONThe combined filtrates are mixed with 1.5 l of water and neutralized under agitation by the addition of solid sodium bicarbonate
  5. 5
    WaschenThe organic phase is then washed with water
  6. 6
    Trocknendried over sodium sulfate
  7. 7
    Einengenconcentrated under vacuum

Vorschrift

A solution of 196 g of 7α-chloro-5,6β-epoxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one in 500 ml of acetic acid and 800 ml of tetrahydrofuran is combined at 70° C. with 392 g of zinc dust in two portions at an interval of 30 minutes, and stirred for one hour at this temperature. After cooling, the zinc is filtered off over "Celite" and washed with 5 l of methylene chloride. The combined filtrates are mixed with 1.5 l of water and neutralized under agitation by the addition of solid sodium bicarbonate. The organic phase is then washed with water, dried over sodium sulfate, and concentrated under vacuum. By trituration of the thus-obtained solid with ethyl acetate, 134.7 g of 5-hydroxy-15β,16β-methylene-3β-pivaloyloxy-5β-androst-6-en-17-one is produced, mp 243° C.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US04614616uspto-grants-1986_09