Reaction #93689

ord-516606992516484ba946ff4032f48a0b

Reaction equation

c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
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](O)[C@H]3O[C@]32C1
5,6β-epoxy-7β-hydroxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one
ClCCl
dichloromethane
ClC(Cl)(Cl)Cl
tetrachloromethane
→
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

Reactants

c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
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](O)[C@H]3O[C@]32C1
5,6β-epoxy-7β-hydroxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one
ClCCl
dichloromethane
ClC(Cl)(Cl)Cl
tetrachloromethane

Reagents

None

Solvents

c1ccncc1
pyridine

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    WashThe reaction solution is washed with water
  2. 2
    Dryingdried over sodium sulfate
  3. 3
    Otherevaporated to dryness under vacuum
  4. 4
    workup.STIRRINGThe residue is stirred up with 310 ml of ethanol
  5. 5
    Filtrationfiltered
  6. 6
    WashThe filter cake is washed with 175 ml of ethanol
  7. 7
    Otherdried under vacuum

Procedure

A solution of 169 g of 5,6β-epoxy-7β-hydroxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one in a mixture of respectively 340 ml of dichloromethane, tetrachloromethane, and pyridine is combined with 200 g of triphenylphosphine and stirred for 2 hours at room temperature. The reaction solution is washed with water, dried over sodium sulfate, and evaporated to dryness under vacuum. The residue is stirred up with 310 ml of ethanol and filtered. The filter cake is washed with 175 ml of ethanol and dried under vacuum, thus obtaining 139.2 g of 7α-chloro-5,6β-epoxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one. An analytical sample, recrystallized from acetone-hexane, has a melting point of 228° C. [α]D =-100° (chloroform).

Source

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