Water → 21-Acetoxy-6alpha-chloro-16alpha-methyl-1,4,9(11)-pregnatriene-3,20-dione

HRID 1577861Notes

Reaction equation

HRID 1577861 reaction equation
[C:1]([O:4][CH2:5][C:6](=[O:30])[C@@H:7]1[C@:24]2([CH3:25])[C@H:10]([C@H:11]3[C@H:21]([C@@H:22](O)[CH2:23]2)[C@:19]2([CH3:20])[C:14](=[CH:15][C:16](=[O:27])[CH:17]=[CH:18]2)[C@@H:13]([Cl:28])[CH2:12]3)[CH2:9][C@H:8]1[CH3:29])(=[O:3])[CH3:2].CS(Cl)(=O)=O.O>N1C(C)=CC(C)=CC=1C.CN(C=O)C>[C:1]([O:4][CH2:5][C:6](=[O:30])[C@@H:7]1[C@:24]2([CH3:25])[C@H:10]([C@H:11]3[C:21](=[CH:22][CH2:23]2)[C@:19]2([CH3:20])[C:14](=[CH:15][C:16](=[O:27])[CH:17]=[CH:18]2)[C@@H:13]([Cl:28])[CH2:12]3)[CH2:9][C@H:8]1[CH3:29])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 962WaterHCID 31297Methanesulfonyl chlorideHCID 7051826521-Acetoxy-6alpha-chloro-11beta-hydroxy-16alpha-methyl-1,4-pregnadiene-3,20-dione

Product 1

HCID 2281743021-Acetoxy-6alpha-chloro-16alpha-methyl-1,4,9(11)-pregnatriene-3,20-dioneYield 90.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 79532,4,6-TrimethylpyridineSolvent

Procedure

A solution of 14.0 g of 21-acetoxy-6α-chloro-11β-hydroxy-16α-methyl-1,4-pregnadiene-3,20-dione in 29 ml of collidine and 90 ml of DMF is combined with 11 ml of methanesulfonic acid chloride containing 3% sulfur dioxide and agitated at room temperature. After 15 minutes, 15 ml of water is added under ice cooling. The thus-obtained precipitate is filtered off, washed with water, and dried in the open air. The crude product is chromatographed on silica gel. With 33-61% ethyl acetate-hexane, 12.1 g of 21-acetoxy-6α-chloro-16α-methyl-1,4,9(11)-pregnatriene-3,20-dione is obtained. A sample, recrystallized from ethyl acetate-hexane, melts at 181° C. [α]D25 =+22° (chloroform).

Workup

  1. filtrationThe thus-obtained precipitate is filtered off
  2. washwashed with water
  3. customdried in the open air
  4. customThe crude product is chromatographed on silica gel

Sources & evidence

ORD record
ord-81c4bad37d0e402091dd5cda5818a580
Source dataset
uspto-grants-1981_09
Patent number
US04289763

Reaction notes

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