Water → (15alpha,16alpha)-15,16-Dihydro-3-methoxy-3′H-cycloprop[15,16]androsta-3,5,15-trien-17-one

HRID 2098264Notes

Reaction equation

HRID 2098264 reaction equation
[I-].[CH3:2][S+](C)(C)=O.[OH-].[K+].C(O[C@@H:13]1[C@H:18]2[C@H:19]3[C@H:29]([CH2:30][CH2:31][C@:16]2([CH3:17])[C:15](=[O:34])[CH2:14]1)[C@:27]1([CH3:28])[C:22]([CH:23]=[C:24]([O:32][CH3:33])[CH2:25][CH2:26]1)=[CH:21][CH2:20]3)(=O)C.O>CS(C)=O>[CH2:2]1[C@@H:14]2[C:15](=[O:34])[C@:16]3([CH2:31][CH2:30][C@H:29]4[C@@H:19]([CH2:20][CH:21]=[C:22]5[C@:27]4([CH3:28])[CH2:26][CH2:25][C:24]([O:32][CH3:33])=[CH:23]5)[C@@H:18]3[C@H:13]12)[CH3:17]

Participants

6

Reactant 4

HCID 962WaterHCID 14797Potassium HydroxideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 54571005(15alpha)-15-(Acetyloxy)-3-methoxyandrosta-3,5-dien-17-one

Product 1

HCID 14031648(15alpha,16alpha)-15,16-Dihydro-3-methoxy-3′H-cycloprop[15,16]androsta-3,5,15-trien-17-one

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

64.8 g of trimethylsulfoxonium iodide is dissolved in 900 ml of dimethyl sulfoxide under nitrogen atmosphere with stirring and to this solution 27.55 g of potassium hydroxide is added at 25-30° C. The reaction mixture is stirred for 1 hour, then 81.1 g of 15α-acetoxy-3-methoxy-androst-3,5-diene-17-one is added and stirring is continued at 25-30° C. until the reaction is finished (about additional 6 hours). The solution is slowly added to 4500 ml of water, the precipitate is compacted by stirring (30 minutes), filtered, washed with water until it is neutral and dried in vacuo to constant weight below 40° C. The title compound is crystallized from methanol.

Workup

  1. additionis added at 25-30° C
  2. stirringstirring
  3. customis continued at 25-30° C. until the reaction
  4. customabout additional 6 hours
  5. stirringby stirring (30 minutes)
  6. filtrationfiltered
  7. washwashed with water until it
  8. customdried in vacuo to constant weight below 40° C
  9. customThe title compound is crystallized from methanol

Sources & evidence

ORD record
ord-1e71f56193dc4b1f950f2db610eb62e2
Source dataset
uspto-grants-2013_05
Patent number
US08450476B2

Reaction notes

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