17,21-Bis(acetyloxy)pregn-4-ene-3,20-dione → 17,21-Diacetoxy-6-methylene-4-pregnene-3,20-dione

HRID 2059159Notes

Reaction equation

HRID 2059159 reaction equation
[C:1]([O-])(=O)C.[Na+].[C:6]([O:9][C@:10]1([C@:34]2([CH3:35])[C@H:20]([C@H:21]3[C@H:31]([CH2:32][CH2:33]2)[C@:29]2([CH3:30])[C:24](=[CH:25][C:26](=[O:36])[CH2:27][CH2:28]2)[CH2:23][CH2:22]3)[CH2:19][CH2:18]1)[C:11](=[O:17])[CH2:12][O:13][C:14](=[O:16])[CH3:15])(=[O:8])[CH3:7]>C(Cl)Cl.COCOC.P(Cl)(Cl)(Cl)=O.O>[C:6]([O:9][C@:10]1([C@:34]2([CH3:35])[C@H:20]([C@H:21]3[C@H:31]([CH2:32][CH2:33]2)[C@:29]2([CH3:30])[C:24](=[CH:25][C:26](=[O:36])[CH2:27][CH2:28]2)[C:23](=[CH2:1])[CH2:22]3)[CH2:19][CH2:18]1)[C:11](=[O:17])[CH2:12][O:13][C:14](=[O:16])[CH3:15])(=[O:8])[CH3:7]

Participants

7

Reactant 2

HCID 10216517,21-Bis(acetyloxy)pregn-4-ene-3,20-dioneHCID 517045Sodium Acetate

Product 1

HCID 1295177117,21-Diacetoxy-6-methylene-4-pregnene-3,20-dioneYield 80.3%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 8020DimethoxymethaneSolventHCID 24813Phosphorus oxychlorideSolvent

Procedure

A suspension of 1.0 g of sodium acetate in 30 ml of methylene chloride, 30 ml of formaldehyde dimethylacetal and 3.8 ml of phosphorus oxychloride is combined with 1.0 g of 17,21-diacetoxy-4-pregnene-3,20-dione and refluxed for 35 hours under agitation. After cooling to room temperature, the mixture is diluted with methylene chloride and water. Under stirring, a saturated soda solution is added dropwise until an alkaline reaction of the aqueous phase has been obtained. The organic phase is separated, washed with water, dried over sodium sulfate, and evaporated under vacuum. Finally, the product is recrystallized from acetone/hexane, thus isolating 825 mg of 17,21-diacetoxy-6-methylene-4-pregnene-3,20-dione, mp 227°-228° C.

Workup

  1. temperaturerefluxed for 35 hours under agitation
  2. additiona saturated soda solution is added dropwise until an alkaline reaction of the aqueous phase
  3. customhas been obtained
  4. customThe organic phase is separated
  5. washwashed with water
  6. dry with materialdried over sodium sulfate
  7. customevaporated under vacuum
  8. customFinally, the product is recrystallized from acetone/hexane

Sources & evidence

ORD record
ord-094349ab36a643188f1add06d1972016
Source dataset
uspto-grants-1982_03
Patent number
US04322349

Reaction notes

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