Phosphorus oxychloride → HCID 13477372, compound

HRID 868168Notes

Reaction equation

HRID 868168 reaction equation
[C:1]([O-])(=O)C.[Na+].P(Cl)(Cl)(Cl)=O.[OH:11][C@:12]1([C@:32]2([CH3:33])[C@H:18]([C@H:19]3[C:29](=[CH:30][CH2:31]2)[C@:27]2([CH3:28])[C:22](=[CH:23][C:24](=[O:34])[CH2:25][CH2:26]2)[CH2:21][CH2:20]3)[CH2:17][C@@H:16]1[CH3:35])[C:13](=[O:15])[CH3:14]>C(Cl)(Cl)Cl.COCOC>[OH:11][C@:12]1([C@:32]2([CH3:33])[C@H:18]([C@H:19]3[C:29](=[CH:30][CH2:31]2)[C@:27]2([CH3:28])[C:22](=[CH:23][C:24](=[O:34])[CH2:25][CH2:26]2)[C:21](=[CH2:1])[CH2:20]3)[CH2:17][C@@H:16]1[CH3:35])[C:13](=[O:15])[CH3:14]

Participants

6

Reactant 3

HCID 24813Phosphorus oxychloride2×HCID 517045Sodium AcetateHCID 13477370HCID 13477370, compound

Product 1

HCID 13477372HCID 13477372, compoundYield 57%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8020DimethoxymethaneSolvent

Conditions

Temperature
65 °C

Procedure

A suspension of 10.0 g of sodium acetate in 300 ml of chloroform and 300 ml of formaldehyde dimethylacetal is stirred with 19 ml of phosphorus oxychloride for one hour at a bath temperature of 65° C. After adding 10.0 g of 17α-hydroxy-16β-methyl-4,9(11)-pregnadiene-3,20-dione, another 19 ml of phosphorus oxychloride is added dropwise and the reaction solution is stirred for another 6.5 hours at 65° C. The cooled-off solution is treated with such an amount of a saturated soda solution that the aqueous phase is made permanently alkaline. The organic phase is separated, washed neutral and concentrated after drying. The crude product is purified on 700 g of silica gel with a hexane-ethyl acetate gradient (0-50% ethyl acetate), thus isolating 5.9 g of 17α-hydroxy-16β-methyl-6-methylene-4,9(11)-pregnadiene-3,20-dione, mp 157°-158° C.

Workup

  1. additionThe cooled-off solution is treated with such an amount of a saturated soda solution that the aqueous phase
  2. customThe organic phase is separated
  3. washwashed neutral
  4. concentrationconcentrated
  5. customafter drying
  6. customThe crude product is purified on 700 g of silica gel with a hexane-ethyl acetate gradient (0-50% ethyl acetate)

Sources & evidence

ORD record
ord-aa06e7dc3f4f466ca3129adcbfcb0df6
Source dataset
uspto-grants-1988_10
Patent number
US04777165

Reaction notes

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