Triethylamine → 20,20-Ethylenedioxy-3alpha-hydroxy-2alpha-methyl-5alpha-pregnane-11-one

HRID 1606488Notes

Reaction equation

HRID 1606488 reaction equation
P(OC)(OC)OC.C(N(CC)CC)C.[CH2:15]1[CH2:42][O:41][C:17]([C@@H:19]2[C@:36]3([CH3:37])[C@H:22]([C@H:23]4[C@H:33]([C:34](=[O:38])[CH2:35]3)[C@:31]3([CH3:32])[C@H:26]([CH2:27][C:28](=[O:40])[C@@H:29]([CH3:39])[CH2:30]3)[CH2:25][CH2:24]4)[CH2:21][CH2:20]2)([CH3:18])[O:16]1>C(O)(C)C.O.Cl.Cl.Cl[Ir](Cl)(Cl)Cl>[CH2:42]1[CH2:15][O:16][C:17]([C@@H:19]2[C@:36]3([CH3:37])[C@H:22]([C@H:23]4[C@H:33]([C:34](=[O:38])[CH2:35]3)[C@:31]3([CH3:32])[C@H:26]([CH2:27][C@H:28]([OH:40])[C@H:29]([CH3:39])[CH2:30]3)[CH2:25][CH2:24]4)[CH2:21][CH2:20]2)([CH3:18])[O:41]1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 8472Trimethyl phosphiteHCID 8673333220,20-Ethylenedioxy-2beta-methyl-5alpha-pregnane-3,11-dione

Product 1

HCID 7058512720,20-Ethylenedioxy-3alpha-hydroxy-2alpha-methyl-5alpha-pregnane-11-oneYield 63.3%

Reagents, catalysts & solvents 2

HCID 16211483Tetrachloroiridium--hydrogen chloride--water (1/2/1)CatalystHCID 3776IsopropanolSolvent

Procedure

A solution of chloroiridic acid (10 mg.) and trimethyl phosphite (1.5 ml.) in aqueous 90% isopropanol (20 ml.) was heated under reflux for 17 hours. The solution was then neutralised with triethylamine, 20,20-ethylenedioxy-2β-methyl-5α-pregnane-3,11-dione (0.66 g.) was added, and the mixture was heated under reflux for 48 hr. The reaction mixture was cooled and partitioned between methylene chloride and water. The organic layer was dried (MgSO4) and evaporated in vacuo. The residue (0.69 g.) was purified by preparative layer chromatography and crystallised from methyl acetate/petroleum ether (b.p. 60°-80°) to give 20,20-ethylenedioxy-3α-hydroxy-2α-methyl-5α-pregnan-11-one (0.42 g.), m.p. 167°-168°, [α]D + 68°.

Workup

  1. temperatureunder reflux for 17 hours
  2. additionwas added
  3. temperaturethe mixture was heated
  4. temperatureunder reflux for 48 hr
  5. temperatureThe reaction mixture was cooled
  6. custompartitioned between methylene chloride and water
  7. dry with materialThe organic layer was dried (MgSO4)
  8. customevaporated in vacuo
  9. customThe residue (0.69 g.) was purified by preparative layer chromatography
  10. customcrystallised from methyl acetate/petroleum ether (b.p. 60°-80°)

Sources & evidence

ORD record
ord-390ef995a30c4c33a80453265931943e
Source dataset
uspto-grants-1976_04
Patent number
US03953429

Reaction notes

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