7alpha-Chloro-5,6beta-epoxy-15beta,16beta-methylen-3beta-pivaloyloxy-5beta-androstan-17-one → 5-Hydroxy-15 beta,16 beta-methylene-3 beta-pivaloyloxy-5 beta-androst-6-en-17-one

HRID 65412Notes

Reaction equation

HRID 65412 reaction equation
Cl[C@@H:2]1[C@H:19]2[O:20][C@:18]32[C@:13]([CH3:28])([CH2:14][CH2:15][C@H:16]([O:21][C:22](=[O:27])[C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:17]3)[C@@H:12]2[C@@H:3]1[C@H:4]1[C@@:8]([CH2:10][CH2:11]2)([CH3:9])[C:7](=[O:29])[C@H:6]2[CH2:30][C@@H:5]12>C(O)(=O)C.O1CCCC1.[Zn]>[OH:20][C@@:18]12[CH2:17][C@@H:16]([O:21][C:22](=[O:27])[C:23]([CH3:24])([CH3:25])[CH3:26])[CH2:15][CH2:14][C@:13]1([CH3:28])[C@@H:12]1[C@H:3]([C@H:4]3[C@@:8]([CH2:10][CH2:11]1)([CH3:9])[C:7](=[O:29])[C@H:6]1[CH2:30][C@@H:5]31)[CH:2]=[CH:19]2

Participants

5

Reactant 1

HCID 130759607alpha-Chloro-5,6beta-epoxy-15beta,16beta-methylen-3beta-pivaloyloxy-5beta-androstan-17-one

Product 1

HCID 130759725-Hydroxy-15 beta,16 beta-methylene-3 beta-pivaloyloxy-5 beta-androst-6-en-17-oneYield 74.6%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

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.

Workup

  1. temperatureAfter cooling
  2. filtrationthe zinc is filtered off over "Celite"
  3. washwashed with 5 l of methylene chloride
  4. additionThe combined filtrates are mixed with 1.5 l of water and neutralized under agitation by the addition of solid sodium bicarbonate
  5. washThe organic phase is then washed with water
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-88e04718e1d44870854fe8070f599930
Source dataset
uspto-grants-1986_09
Patent number
US04614616

Reaction notes

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