Reaction #93694

ord-4f6f033bf183440a905cf0a17ebf7a0c

Reaction equation

C[C@]12CC[C@H]3[C@@H]([C@H](Cl)[C@H]4O[C@]45C[C@@H](O)CC[C@]35C)[C@@H]1[C@@H]1C[C@@H]1C2=O
7α-chloro-5,6β-epoxy-3β-hydroxy-15β,16β-methylene-5β-androstan-17-one
C1CCOC1
tetrahydrofuran
→
C[C@]12CC[C@H]3[C@@H](C=C[C@]4(O)C[C@@H](O)CC[C@]34C)[C@@H]1[C@@H]1C[C@@H]1C2=O
3β,5-dihydroxy-15β,16β-methylene-5β-androst-6-en-17-one
Yield 94.4%

Reactants

C[C@]12CC[C@H]3[C@@H]([C@H](Cl)[C@H]4O[C@]45C[C@@H](O)CC[C@]35C)[C@@H]1[C@@H]1C[C@@H]1C2=O
7α-chloro-5,6β-epoxy-3β-hydroxy-15β,16β-methylene-5β-androstan-17-one
C1CCOC1
tetrahydrofuran

Reagents

[Zn]
zinc

Solvents

CC(=O)O
acetic acid

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    FiltrationThe zinc is then filtered off
  2. 2
    workup.ADDITIONthe filtrate is diluted with methylene chloride
  3. 3
    Washwashed with sodium bicarbonate solution and water
  4. 4
    DryingAfter drying over sodium sulfate
  5. 5
    Concentrationthe product is concentrated under vacuum

Procedure

107.5 g of 7α-chloro-5,6β-epoxy-3β-hydroxy-15β,16β-methylene-5β-androstan-17-one is dissolved in 500 ml of acetic acid and 500 ml of tetrahydrofuran and, after the addition of 324 g of zinc dust in three portions, stirred at room temperature for 16 hours. The zinc is then filtered off, the filtrate is diluted with methylene chloride, and washed with sodium bicarbonate solution and water. After drying over sodium sulfate, the product is concentrated under vacuum. By trituration of the thus-obtained solid with ethyl acetate, 91.5 g of 3β,5-dihydroxy-15β,16β-methylene-5β-androst-6-en-17-one is produced, mp 196° C.

Source

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