p-Toluenesulfonic acid → (8S,10R,13S,14S)-3-methoxy-10,13-dimethyl-1,2,7,8,12,14,15,16-octahydrocyclopenta[a]phenanthren-17-one

HRID 1032029Notes

Reaction equation

HRID 1032029 reaction equation
[CH3:1][C@:2]12[CH2:19][CH:18]=[C:17]3[C@@H:7]([CH2:8][CH2:9][C:10]4[C@:15]3([CH3:16])[CH2:14][CH2:13][C:12](=[O:20])[CH:11]=4)[C@@H:6]1[CH2:5][CH2:4][C:3]2=[O:21].O1CCOC[CH2:23]1.COC(OC)OC.C1(C)C=CC(S(O)(=O)=O)=CC=1>N1C=CC=CC=1>[CH3:23][O:20][C:12]1[CH2:13][CH2:14][C@@:15]2([CH3:16])[C:10](=[CH:9][CH2:8][C@@H:7]3[C:17]2=[CH:18][CH2:19][C@@:2]2([CH3:1])[C@H:6]3[CH2:5][CH2:4][C:3]2=[O:21])[CH:11]=1

Participants

6

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 9005Trimethyl orthoformateHCID 312751,4-DioxaneHCID 2395959-Dehydroandrostenedione

Product 1

HCID 13037635(8S,10R,13S,14S)-3-methoxy-10,13-dimethyl-1,2,7,8,12,14,15,16-octahydrocyclopenta[a]phenanthren-17-one

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

11.5 g of 4,9(11)-androstadiene-3,17-dione [U.S. Pat. No. 3,441,559 (1969)]in 200 ml of dioxane is reacted with 20 ml of orthoformic acid trimethyl ester and 100 mg of p-toluenesulfonic acid. After 48 hours, 5 ml of pyridine is added to the solution, the latter is concentrated under vacuum, the residue taken up in ethyl acetate, washed with water, and dried over sodium sulfate. After chromatography of the crude product with a hexane-ethyl acetate gradient on silica gel containing 2% triethylamine, 9.2 g of 3-methoxy-3,5,9(11)-androstatrien-17-one is isolated; mp 153.4° C.

Workup

  1. concentrationthe latter is concentrated under vacuum
  2. washwashed with water
  3. dry with materialdried over sodium sulfate

Sources & evidence

ORD record
ord-8f7441fe1ee14c1497a8aab338e52dc6
Source dataset
uspto-grants-1990_09
Patent number
US04956482

Reaction notes

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