Phosphorus oxychloride → HCID 86738310、化合物

HRID 2059166ノート

反応式

HRID 2059166 の反応式
[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]

参加物

6

反応物 3

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

生成物 1

HCID 86738310HCID 86738310、化合物収率 60.9%

試薬・触媒・溶媒 2

HCID 6212Chloroform溶媒HCID 8020Dimethoxymethane溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-1113561cd7984fb5830d34bc2a69663a
出典データセット
uspto-grants-1982_03
特許番号
US04322349

反応ノート

読み込み中…