反応 #93690

ord-88e04718e1d44870854fe8070f599930

反応方程式

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
収率 74.6%

反応物

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

試薬

[Zn]
zinc

溶媒

CC(=O)O
acetic acid
C1CCOC1
tetrahydrofuran

反応条件

詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    温度After cooling
  2. 2
    ろ過the zinc is filtered off over "Celite"
  3. 3
    洗浄washed 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
    洗浄The organic phase is then washed with water
  6. 6
    乾燥dried over sodium sulfate
  7. 7
    濃縮concentrated under vacuum

実験手順

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.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US04614616uspto-grants-1986_09