Reacción #93690

ord-88e04718e1d44870854fe8070f599930

Ecuación de reacción

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
Rendimiento 74.6%

Reactantes

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

Reactivos

[Zn]
zinc

Disolventes

CC(=O)O
acetic acid
C1CCOC1
tetrahydrofuran

Condiciones de reacción

Condiciones detalladas
See reaction.notes.procedure_details.

Tratamiento posterior

  1. 1
    TemperaturaAfter cooling
  2. 2
    Filtraciónthe zinc is filtered off over "Celite"
  3. 3
    Lavadowashed 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
    LavadoThe organic phase is then washed with water
  6. 6
    Secadodried over sodium sulfate
  7. 7
    Concentraciónconcentrated under vacuum

Procedimiento

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.

Fuente

DOI: 10.6084/m9.figshare.5104873.v1Patente: US04614616uspto-grants-1986_09