Ammonium Chloride → (7alpha,17beta)-17-(Acetyloxy)-7-ethenylestr-4-en-3-one

HRID 1815782ノート

反応式

HRID 1815782 の反応式
[C:1]([O:4][C@H:5]1[CH2:10][CH2:9][C@H:8]2[C@H:11]3[C@H:20]([CH2:21][CH2:22][C@:6]12[CH3:7])[C@@H:19]1[C:14](=[CH:15][C:16](=[O:23])[CH2:17][CH2:18]1)[CH:13]=[CH:12]3)(=[O:3])[CH3:2].[Br-].[Li+].[S-][C:27]1C=CC=C[CH:28]=1.[Li+].[Cl-].[NH4+]>O1CCCC1>[C:1]([O:4][C@H:5]1[CH2:10][CH2:9][C@H:8]2[C@H:11]3[C@H:20]([CH2:21][CH2:22][C@:6]12[CH3:7])[C@@H:19]1[C:14](=[CH:15][C:16](=[O:23])[CH2:17][CH2:18]1)[CH2:13][C@H:12]3[CH:27]=[CH2:28])(=[O:3])[CH3:2]

参加物

6

反応物 4

HCID 25517Ammonium ChlorideHCID 82050Lithium BromideHCID 10975459Lithium thiophenolateHCID 11088332(17beta)-3-Oxoestra-4,6-dien-17-yl acetate

生成物 1

HCID 69788950(7alpha,17beta)-17-(Acetyloxy)-7-ethenylestr-4-en-3-one

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
-15 °C

実験手順

—Vinylmagnesium chloride in tetrahydrofuran (2 M, 159.2 ml) was added dropwise to a mixture of (17β)-17-(acetyloxy)estra-4,6-diene-3-one [Syntex, DE 1143199 (1963); 50.0 g], copper(I) bromide-dimethyl sulfide complex (3.18 g), lithium bromide (1.38 g), and lithium thiophenoxide (16 ml of a 1 M solution in tetrahydrofuran), in dry tetrahydrofuran (167 ml), cooled to −15° C. After 30 min. stirring a saturated aqueous solution of ammonium chloride was added and the product extracted into ethyl acetate. The combined organic phases were concentrated under reduced pressure whereafter the residue was dissolved in acetone (1000 ml) and treated with hydrochloric acid (4 M, 100 ml). After 30 min. stirring at room temperature, the mixture was poured into a saturated aqueous solution of sodium hydrogencarbonate. Part of the acetone was removed under reduced pressure and the product was extracted into ethyl acetate. The combined organic phases were washed with brine, dried over sodium sulfate and concentrated under reduced pressure, to give (7α,17β)-17-(acetyloxy)-7-ethenylestr-4-en-3-one (59.4 g). The product was used in the following step without further purification.

後処理

  1. additionwas added
  2. extractionthe product extracted into ethyl acetate
  3. concentrationThe combined organic phases were concentrated under reduced pressure whereafter the residue
  4. dissolutionwas dissolved in acetone (1000 ml)
  5. additiontreated with hydrochloric acid (4 M, 100 ml)
  6. additionthe mixture was poured into a saturated aqueous solution of sodium hydrogencarbonate
  7. customPart of the acetone was removed under reduced pressure
  8. extractionthe product was extracted into ethyl acetate
  9. washThe combined organic phases were washed with brine
  10. dry with materialdried over sodium sulfate
  11. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-4b5c7b63bac44d1283d7a38696a20905
出典データセット
uspto-grants-2005_04
特許番号
US06881728B1

反応ノート

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