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

HRID 353703

Reaktionsgleichung

Reaktionsgleichung von HRID 353703
[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, 9.55 ml) was added dropwise to a mixture of (17β)-17-(acetyloxy)estra-4,6-dien-3-one (Example 3, step i; 3.0 g), copper(I) bromide-dimethyl sulfide complex (0.191 g), lithium bromide (0.083 g), and lithium thiophenoxide (0.96 ml of a 1 M solution in tetrahydrofuran), in dry tetrahydrofuran (10 ml), cooled to −15° C. After 25 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 (100 ml) and treated with hydrochloric acid (4 M, 10 ml). After 30 min. stirring at room temperature, a saturated aqueous solution of sodium hydrogencarbonate was added. 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 (3.76 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 (100 ml)
  5. additiontreated with hydrochloric acid (4 M, 10 ml)
  6. additiona saturated aqueous solution of sodium hydrogencarbonate was added
  7. extractionThe product was extracted into ethyl acetate
  8. washthe combined organic phases were washed with brine
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-2a8da3a9ab92436fa0175ed14566811d
Quelldatensatz
uspto-grants-2004_06
Patentnummer
US06756366B1

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