Water → 3-Chloromethylene-19-methylthio-4-androsten-17-one

HRID 1650785Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1650785
[CH3:1][S:2][CH2:3][C@@:4]12[C@@H:21]3[C@H:12]([C@H:13]4[C@@:17]([CH2:19][CH2:20]3)([CH3:18])[C:16](=[O:22])[CH2:15][CH2:14]4)[CH2:11][CH2:10][C:9]1=[CH:8][C:7](=O)[CH2:6][CH2:5]2.[Cl-].[Cl:25][CH2:26][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C([Li])CCC.O>O1CCCC1.CCOCC>[Cl:25][CH:26]=[C:7]1[CH2:6][CH2:5][C@@:4]2([CH2:3][S:2][CH3:1])[C:9]([CH2:10][CH2:11][C@@H:12]3[C@@H:21]2[CH2:20][CH2:19][C@@:17]2([CH3:18])[C@H:13]3[CH2:14][CH2:15][C:16]2=[O:22])=[CH:8]1

Komponenten

7

Edukt 4

HCID 962WaterHCID 14614219-Thiomethylandrost-4-ene-3,17-dioneHCID 197823(Chloromethyl)triphenylphosphonium chlorideHCID 178418339Butyllithium

Produkt 1

HCID 545684673-Chloromethylene-19-methylthio-4-androsten-17-oneAusbeute 49,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

500 mg of 19-methylthio-4-androstene-3,17-dione (European patent 100,566) is added to a suspension of 5.21 g of chloromethyl triphenylphosphonium chloride in 50 ml of tetrahydrofuran, which was stirred with 9.5 ml of (1.6 m of butyllithium in ether) 0.5 hours at 20° C., and stirred for 30 minutes at 0° C. Then it is mixed with water, extracted three times with ethyl acetate, washed neutral, dried on sodium sulfate and concentrated to dryness. 995 mg of raw product is obtained, which after chromatographic purification yields 273 mg of pure 3-chloromethylene-19-methylthio-4-androsten-17-one with a melting point of 114°-115° C., [α]D +241.5° C. (CHCl3), as pure E form.

Aufarbeitung

  1. extractionextracted three times with ethyl acetate
  2. washwashed neutral
  3. customdried on sodium sulfate
  4. concentrationconcentrated to dryness
  5. custom995 mg of raw product is obtained
  6. customwhich after chromatographic purification

Quellen und Nachweise

ORD-Eintrag
ord-c2c3cbc1c3e34d9fb391d0b27f0343a3
Quelldatensatz
uspto-grants-1990_05
Patentnummer
US04925834

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