Phosphorus oxychloride → HCID 86738310, compound

HRID 2059166Notes

Reaction equation

HRID 2059166 reaction equation
[C:1]([O-])(=O)C.[Na+].P(Cl)(Cl)(Cl)=O.[C:11]([O:14][C@@:15]1([C:35]#[CH:36])[CH2:20][CH2:19][C@H:18]2[C@H:21]3[C@H:31]([CH2:32][CH2:33][C@:16]12[CH3:17])[C@:29]1([CH3:30])[C:24](=[CH:25][C:26](=[O:34])[CH2:27][CH2:28]1)[CH2:23][CH2:22]3)(=[O:13])[CH3:12]>C(Cl)(Cl)Cl.COCOC>[C:11]([O:14][C@@:15]1([C:35]#[CH:36])[CH2:20][CH2:19][C@H:18]2[C@H:21]3[C@H:31]([CH2:32][CH2:33][C@:16]12[CH3:17])[C@:29]1([CH3:30])[C:24](=[CH:25][C:26](=[O:34])[CH2:27][CH2:28]1)[C:23](=[CH2:1])[CH2:22]3)(=[O:13])[CH3:12]

Participants

6

Reactant 3

HCID 24813Phosphorus oxychloride2×HCID 517045Sodium AcetateHCID 118695632542-26-9

Product 1

HCID 86738310HCID 86738310, compoundYield 60.9%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8020DimethoxymethaneSolvent

Procedure

A suspension of 1.0 g of sodium acetate in 30 ml of chloroform and 30 ml of methylal is combined with 1.9 ml of phosphorus oxychloride and refluxed for 1 hour. The reaction mixture is combined with 1.0 g of 17β-acetoxy-17α-ethynyl-4-androsten-3-one and, under reflux, 1.9 ml of phosphorus oxychloride is added dropwise within 2 hours. The mixture is refluxed for 1 hour, cooled, and rendered alkaline by the dropwise addition of saturated soda solution. The organic phase is separated and concentrated under vacuum. For working-up purposes, the crude product is mixed with a small amount of methylene chloride and water, as well as 5 g of soda. After steam distillation, the product is vacuum-filtered, the residue washed neutral with water, and purified on 105 g of silica gel with a hexane/ethyl acetate gradient (0-50% ethyl acetate). In this way, 630 mg of 17β-acetoxy-17α-ethynyl-6-methylene-4-androsten-3-one is isolated, mp 158°-160° C.

Workup

  1. temperaturerefluxed for 1 hour
  2. temperatureunder reflux
  3. temperatureThe mixture is refluxed for 1 hour
  4. temperaturecooled
  5. additionby the dropwise addition of saturated soda solution
  6. customThe organic phase is separated
  7. concentrationconcentrated under vacuum
  8. additionthe crude product is mixed with a small amount of methylene chloride and water
  9. distillationAfter steam distillation
  10. filtrationthe product is vacuum-filtered
  11. washthe residue washed neutral with water
  12. custompurified on 105 g of silica gel with a hexane/ethyl acetate gradient (0-50% ethyl acetate)

Sources & evidence

ORD record
ord-1113561cd7984fb5830d34bc2a69663a
Source dataset
uspto-grants-1982_03
Patent number
US04322349

Reaction notes

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