Phosphorus oxychloride → 21-Acetoxy-17alpha-hydroxy-6-methylene-4-pregnene-3,20-dione

HRID 2059165Notes

Reaction equation

HRID 2059165 reaction equation
[C:1]([O:4][CH2:5][C:6](=[O:28])[C@:7]1([OH:27])[C@:24]2([CH3:25])[C@H:10]([C@H:11]3[C@H:21]([CH2:22][CH2:23]2)[C@:19]2([CH3:20])[C:14](=[CH:15][C:16](=[O:26])[CH2:17][CH2:18]2)[CH2:13][CH2:12]3)[CH2:9][CH2:8]1)(=[O:3])[CH3:2].[C:29]([O-])(=O)C.[Na+].P(Cl)(Cl)(Cl)=O>C(Cl)(Cl)Cl.C(OCOCC)C>[C:1]([O:4][CH2:5][C:6](=[O:28])[C@:7]1([OH:27])[C@:24]2([CH3:25])[C@H:10]([C@H:11]3[C@H:21]([CH2:22][CH2:23]2)[C@:19]2([CH3:20])[C:14](=[CH:15][C:16](=[O:26])[CH2:17][CH2:18]2)[C:13](=[CH2:29])[CH2:12]3)[CH2:9][CH2:8]1)(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 10181611-Deoxycortisol 21-acetateHCID 517045Sodium Acetate

Product 1

HCID 1295179021-Acetoxy-17alpha-hydroxy-6-methylene-4-pregnene-3,20-dioneYield 86.3%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 10024DiethoxymethaneSolvent

Procedure

Analogously to Example 35, 1.0 g of 21-acetoxy-17α-hydroxy-4-pregnene-3,20-dione is stirred with a suspension of 1.0 g of sodium acetate in 30 ml of chloroform, 30 ml of formaldehyde diethylacetal, and 3.8 ml of phosphorus oxychloride for 7 hours at 65° C., and then worked up. The crude product is purified on 220 g of silica gel with a methylene chloride/acetone gradient (0-12% acetone), thus obtaining 890 mg of 21-acetoxy-17α-hydroxy-6-methylene-4-pregnene-3,20-dione, mp 194.5°-196° C.

Workup

  1. customThe crude product is purified on 220 g of silica gel with a methylene chloride/acetone gradient (0-12% acetone)

Sources & evidence

ORD record
ord-05aefbe577c449cfbe499daa621feb4b
Source dataset
uspto-grants-1982_03
Patent number
US04322349

Reaction notes

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