Benzene → 20,20-Ethylenedioxy-3alpha-hydroxy-16alpha-methyl-5alpha-pregnan-11-one

HRID 1701440Notes

Reaction equation

HRID 1701440 reaction equation
[OH:1][C@@H:2]1[CH2:21][CH2:20][C@@:19]2([CH3:22])[C@@H:4]([CH2:5][CH2:6][C@@H:7]3[C@@H:18]2[C:17](=[O:23])[CH2:16][C@@:15]2([CH3:24])[C@H:8]3[CH2:9][C@@H:10]([CH3:25])[C@@H:11]2[C:12](=[O:14])[CH3:13])[CH2:3]1.[CH:26]1[CH:31]=CC=CC=1.O.C1(C)C=CC(S(O)(=O)=[O:40])=CC=1.C(=O)([O-])O.[Na+]>O.C(O)CO>[CH2:26]1[CH2:31][O:40][C:12]([C@@H:11]2[C@:15]3([CH3:24])[C@H:8]([C@H:7]4[C@H:18]([C:17](=[O:23])[CH2:16]3)[C@:19]3([CH3:22])[C@H:4]([CH2:3][C@H:2]([OH:1])[CH2:21][CH2:20]3)[CH2:5][CH2:6]4)[CH2:9][C@H:10]2[CH3:25])([CH3:13])[O:14]1

Participants

7

Reactant 4

HCID 241BenzeneHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 705839113alpha-Hydroxy-16alpha-methyl-5alpha-pregnane-11,20-dione

Product 1

HCID 7058361120,20-Ethylenedioxy-3alpha-hydroxy-16alpha-methyl-5alpha-pregnan-11-one

Reagents, catalysts & solvents 2

HCID 174Ethylene GlycolSolventHCID 962WaterSolvent

Procedure

A mixture of 3α-hydroxy-16α-methyl-5α-pregnane-11,20-dione (1.00 g), benzene (50 ml), ethylene glycol (5 ml) and toluene-4-sulphonic acid monohydrate (50 mg) was brought to reflux under a Dean and Stark water separator and refluxed for 5 hr, then poured into saturated aqueous sodium hydrogen carbonate (50 ml) and the layers separated. The aqueous portion was extracted with additional benzene (50 ml) and the combined organic portions washed with water (2×50 ml), dried and evaporated to a white foam (1.12 g). A portion of this material (1.00 g) was crystallised from ether-petroleum ether (b.p. 60°-80°) to afford the title compound (581 mg), m.p. 122°-124°, [α]D +37.2°.

Workup

  1. temperaturerefluxed for 5 hr
  2. customthe layers separated
  3. extractionThe aqueous portion was extracted with additional benzene (50 ml)
  4. washthe combined organic portions washed with water (2×50 ml)
  5. customdried
  6. customevaporated to a white foam (1.12 g)
  7. customA portion of this material (1.00 g) was crystallised from ether-petroleum ether (b.p. 60°-80°)

Sources & evidence

ORD record
ord-848c10e8d52942b08fabdd3ef261b88b
Source dataset
uspto-grants-1980_03
Patent number
US04192871

Reaction notes

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