반응 #93690

ord-88e04718e1d44870854fe8070f599930

반응 방정식

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
수율 74.6%

반응물

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

시약

[Zn]
zinc

용매

CC(=O)O
acetic acid
C1CCOC1
tetrahydrofuran

반응 조건

상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    온도After cooling
  2. 2
    여과the zinc is filtered off over "Celite"
  3. 3
    세척washed 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
    세척The organic phase is then washed with water
  6. 6
    건조dried over sodium sulfate
  7. 7
    농축concentrated under vacuum

실험 절차

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.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US04614616uspto-grants-1986_09