Diethoxymethane → HCID 18632034, compound

HRID 621619Notes

Reaction equation

HRID 621619 reaction equation
C([O-])(=O)C.[Na+].C(OC[O:10][CH2:11][CH3:12])C.P(Cl)(Cl)(Cl)=O.[CH3:18][C@H:19]1[C@@:36]2([CH3:37])[C:23]([CH2:24][C@@H:25](C)[C@@H:26]3[C@@H:35]2[CH2:34][CH2:33][C@@:31]2([CH3:32])[C@H:27]3[CH2:28][C@@H:29]([F:39])[C:30]2=[O:38])=[CH:22][C:21](=O)[CH2:20]1.C(=O)([O-])[O-].[Na+].[Na+]>C(Cl)(Cl)Cl>[CH3:20][C@H:19]1[C@@:36]2([CH3:37])[C:23]([C:22](=[CH2:21])[C@@H:25]([CH3:24])[C@@H:26]3[C@@H:35]2[CH2:34][CH2:33][C@@:31]2([CH3:32])[C@H:27]3[CH2:28][C@@H:29]([F:39])[C:30]2=[O:38])=[CH:12][C:11](=[O:10])[CH2:18]1

Participants

7

Reactant 5

HCID 10024DiethoxymethaneHCID 10340Sodium CarbonateHCID 24813Phosphorus oxychlorideHCID 517045Sodium AcetateHCID 70377829HCID 70377829, compound

Product 1

HCID 18632034HCID 18632034, 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 1β,7α-dimethyl-16α-fluoroandrost-4-ene-3,17-dione (0.896 g, 2.7 mmol) is stirred at reflux for about 5 hrs, 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. The organic layer is separated, washed to neutrality 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 eluant. Thus the pure 1β,7α-dimethyl-16α-fluoro-6-methylenandrost-4-ene-3,17-dione is obtained in 60% yield (0.56 g).

Workup

  1. temperatureat reflux for about 5 hrs
  2. temperatureto cool
  3. additionis added dropwise until the pH of the aqueous layer
  4. customThe organic layer is separated
  5. washwashed
  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-b829e7f13eaa441892aaf54f03b93cd3
Source dataset
uspto-grants-1989_04
Patent number
US04824830

Reaction notes

Loading…