Diethoxymethane → HCID 66852514, compound

HRID 1905004Notes

Reaction equation

HRID 1905004 reaction equation
[C:1]([O-])(=O)C.[Na+].C(OCOCC)C.P(Cl)(Cl)(Cl)=O.[CH2:18]1[C@@H:20]2[C:21](=[O:39])[CH:22]=[C:23]3[C@:36]([CH3:37])([CH:19]12)[C@@H:35]1[C@H:26]([C@H:27]2[C@@:31]([CH2:33][CH2:34]1)([CH3:32])[C:30](=[O:38])[CH2:29][CH2:28]2)[CH2:25][CH2:24]3.C(=O)([O-])[O-].[Na+].[Na+]>C(Cl)(Cl)Cl>[CH2:1]=[C:24]1[C:23]2[C@:36]([CH3:37])([CH:19]3[CH2:18][C@@H:20]3[C:21](=[O:39])[CH:22]=2)[C@@H:35]2[C@H:26]([C@H:27]3[C@@:31]([CH2:33][CH2:34]2)([CH3:32])[C:30](=[O:38])[CH2:29][CH2:28]3)[CH2:25]1

Participants

7

Reactant 5

HCID 10024DiethoxymethaneHCID 10340Sodium CarbonateHCID 24813Phosphorus oxychlorideHCID 517045Sodium AcetateHCID 13564888HCID 13564888, compound

Product 1

HCID 66852514HCID 66852514, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A mixture of sodium acetate (1 g), absolute chloroform (30 ml), formaldehyde diethyl acetal (30 ml, 0.24 mol), phosphoryl chloride (3.8 ml, 0.04 mol), and 1,2β-methylenandrost-4-en-3,17-dione (0.806 g, 2.7 mmol) is stirred at reflux for about 5 hours, i.e. until the starting material has disappeared. The suspension is allowed to cool and under vigorous stirring a saturated sodium carbonate solution is added dropwise until the pH of the aqueous layer becomes alkaline (ca. 1 hour). The organic layer is separated, neutralized with water, and dried with sodium sulfate. After concentration under reduced pressure the oily residue is purified by chromatography on silica gel using hexane/ethyl acetate as eluent. Thus the pure 6-methylen-1,2β-methylenandrost-4-ene-3,17-dione is obtained in 60% yield (0.194 g).

Workup

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

Sources & evidence

ORD record
ord-da5ae41d31fe46b299efe0c2b5e9a93d
Source dataset
uspto-grants-1989_06
Patent number
US04840943

Reaction notes

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