Dimethyl malonate → HCID 70627270, compound

HRID 839810Notes

Reaction equation

HRID 839810 reaction equation
[C:1]([O:4][C@H:5]1[CH2:25][CH2:24][C@@:23]2([CH3:26])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:22]2[CH2:21][CH2:20][C@@:19]2([CH3:27])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[C:15](=[O:18])[CH2:16][OH:17])[CH2:6]1)(=[O:3])[CH3:2].[C:28](OC)(=[O:34])[CH2:29][C:30]([O:32][CH3:33])=[O:31].[Cl-].[Ca+2].[Cl-]>C1(C)C=CC=CC=1>[C:1]([O:4][C@H:5]1[CH2:25][CH2:24][C@@:23]2([CH3:26])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:22]2[CH2:21][CH2:20][C@@:19]2([CH3:27])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[C:15](=[O:18])[CH2:16][O:17][C:28](=[O:34])[CH2:29][C:30]([O:32][CH3:33])=[O:31])[CH2:6]1)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 7943Dimethyl malonateHCID 5284359Calcium ChlorideHCID 54213239HCID 54213239, compound

Product 1

HCID 70627270HCID 70627270, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
160 °C

Procedure

A mixture of 200 mg of 3β-acetoxy-21-hydroxypregn-5-en-20-one, 10 ml of dimethyl malonate and 2.0 g of calcium chloride was heated in an oil-bath having a temperature of 84° C. for 4 days under nitrogen whereupon 20 ml of toluene was added. The reaction was then arranged for distillation at atmospheric pressure and the bath temperature was raised to 160° C. during 1.5 hours. Subsequently the temperature of the bath temperature was lowered to 84° and the mixture was subjected to distillation at high vacuum for 1.5 hours. The resulting solid residue was dissolved in 15 ml of ether, 2.5 ml of hexane and some charcoal was added. Filtration through diatomaceous earth, followed by concentration of the filtrate with intermittent addition of hexane and ether gave a suspension which after filtration gave 3β-acetoxy-21-[methoxycarbonyl]acetoxy-pregn-5-en-20-one.

Workup

  1. temperaturewas heated in an oil-bath
  2. customa temperature of 84° C.
  3. customfor 4 days
  4. additionwas added
  5. distillationThe reaction was then arranged for distillation at atmospheric pressure
  6. customwas lowered to 84°
  7. distillationthe mixture was subjected to distillation at high vacuum for 1.5 hours
  8. dissolutionThe resulting solid residue was dissolved in 15 ml of ether
  9. addition2.5 ml of hexane and some charcoal was added
  10. filtrationFiltration through diatomaceous earth
  11. additionfollowed by concentration of the filtrate with intermittent addition of hexane and ether
  12. customgave a suspension which
  13. filtrationafter filtration

Sources & evidence

ORD record
ord-01de6d53a91a40bebd3a8458737f2c88
Source dataset
uspto-grants-1978_06
Patent number
US04097477

Reaction notes

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