Diethoxymethane → 1beta-Methyl-6-methylenandrost-4-ene-3,17-dione

HRID 1383025Notes

Reaction equation

HRID 1383025 reaction equation
C([O-])(=O)C.[Na+].C(OC[O:10][CH2:11][CH3:12])C.P(Cl)(Cl)(Cl)=O.C[C@H:19]1[C@@:36]2([CH3:37])[C:23]([CH2:24][CH2:25][C@@H:26]3[C@@H:35]2[CH2:34][CH2:33][C@@:31]2([CH3:32])[C@H:27]3[CH2:28][CH2:29][C:30]2=[O:38])=[CH:22][C:21](=O)[CH2:20]1.C(=O)([O-])[O-].[Na+].[Na+]>C(Cl)(Cl)Cl>[CH3:24][C@H:23]1[C@@:36]2([CH3:37])[C:19]([C:20](=[CH2:21])[CH2:25][C@@H:26]3[C@@H:35]2[CH2:34][CH2:33][C@@:31]2([CH3:32])[C@H:27]3[CH2:28][CH2:29][C:30]2=[O:38])=[CH:12][C:11](=[O:10])[CH2:22]1

Participants

7

Reactant 5

HCID 10024DiethoxymethaneHCID 10340Sodium CarbonateHCID 24813Phosphorus oxychlorideHCID 517045Sodium AcetateHCID 541757841beta-Methyl-4-androstene-3,17-dione

Product 1

HCID 158591201beta-Methyl-6-methylenandrost-4-ene-3,17-dioneYield 60%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A mixture of sodium acetate (1 g), absolute chloroform (30 ml), formaldehyde-diethylacetal (30 ml, 0.24 mol), phosphoryl chloride (3.8 ml, 0.04 mol), and 1β-methylandrost-4-ene-3,17-dione (0.811 g, 2.7 mmol) was stirred at reflux for about 7 hours, i.e. until the starting material had disappeared. The suspension was allowed to cool and under vigorous stirring a saturated sodium carbonate solution was added dropwise until the pH of the aqueous layer became alkaline (~1 hour). The organic layer was separated, neutralized with water, and dried with sodium sulfate. After concentration under reduced pressure the oily residue was purified by chromatography on silica gel using hexane/ethylacetate as eluent. Thus the pure 1β-methyl-6-methylenandrost-4-ene-3,17-dione was obtained in 60% yield (0.195 g); I.R. (KBr): 3100 (6=CH2), 1735 (17-oxo), 1680 (3-oxo), 1630, 1660 cm-1 (Δ4 and 6=CH2).

Workup

  1. temperatureat reflux for about 7 hours
  2. temperatureto cool
  3. additionwas added dropwise until the pH of the aqueous layer
  4. custom(~1 hour)
  5. customThe organic layer was separated
  6. dry with materialdried with sodium sulfate
  7. concentrationAfter concentration under reduced pressure the oily residue
  8. customwas purified by chromatography on silica gel

Sources & evidence

ORD record
ord-2be002a07b40437b937ff1c7a9fb48a4
Source dataset
uspto-grants-1989_02
Patent number
US04808616

Reaction notes

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