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

HRID 1606487Notes

Reaction equation

HRID 1606487 reaction equation
P(OC)(OC)OC.C(N(CC)CC)C.[CH2:15]1[CH2:43][O:42][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:41])[C:29](=[CH:39]O)[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>[CH2:43]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:28](=[O:41])[C@H:29]([CH3:39])[CH2:30]3)[CH2:25][CH2:24]4)[CH2:21][CH2:20]2)([CH3:18])[O:42]1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 8472Trimethyl phosphiteHCID 8673333120,20-Ethylenedioxy 2-hydroxymethylene-5alpha-pregnane-3,11-dione

Product 1

HCID 8673333020,20-Ethylenedioxy-2alpha-methyl-5alpha-pregnane-3,11-dioneYield 6.7%

Reagents, catalysts & solvents 2

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

Procedure

A solution of chloroiridic acid (30 mg.) and trimethyl phosphite (4.5 ml.) in aqueous 90% isopropanol (60 ml.) was heated under reflux for 17 hr. The solution was then neutralised with triethylamine and 20,20-ethylenedioxy 2-hydroxymethylene-5α-pregnane-3,11-dione (2 g.) was added. The mixture was heated under reflux for 40 hr. then cooled and partitioned between water and methylene chloride. The organic layer was dried (MgSO4) and evaporated in vacuo. The residue (1.94 g.) was subjected to preparative t.l.c. giving two fractions. The less polar fraction (0.18 g.) was crystallised from methanol to give 20,20-ethylenedioxy-2α-methyl-5α-pregnane-3,11-dione (0.13 g.), m.p. 179°-180°, [α]D + 77.5°.

Workup

  1. temperatureunder reflux for 17 hr
  2. additionwas added
  3. temperatureThe mixture was heated
  4. temperatureunder reflux for 40 hr
  5. temperaturethen cooled
  6. custompartitioned between water and methylene chloride
  7. dry with materialThe organic layer was dried (MgSO4)
  8. customevaporated in vacuo
  9. customgiving two fractions
  10. customThe less polar fraction (0.18 g.) was crystallised from methanol

Sources & evidence

ORD record
ord-697ca9dfd62f4d70aedfd9132700c478
Source dataset
uspto-grants-1976_04
Patent number
US03953429

Reaction notes

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