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

HRID 1815782

Reaktionsgleichung

Reaktionsgleichung von HRID 1815782
[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]

Komponenten

6

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
-15 °C

Versuchsvorschrift

—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.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-4b5c7b63bac44d1283d7a38696a20905
Quelldatensatz
uspto-grants-2005_04
Patentnummer
US06881728B1

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