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Phosphate → 16-(Phenylsulfinylmethyl)pregn-1,4,9(11),16-tetraene-3,20-dione

HRID 1285315
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1285315
[C:1]1([S:7](Cl)=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:10]([C@:13]1(O)[C:18](=[CH2:19])[CH2:17][C@H:16]2[C@H:20]3[C:30](=[CH:31][CH2:32][C@:14]12[CH3:15])[C@:28]1([CH3:29])[C:23](=[CH:24][C:25](=[O:33])[CH:26]=[CH:27]1)[CH2:22][CH2:21]3)(=[O:12])[CH3:11].P([O-])([O-])([O-])=O>C(Cl)Cl.C(N(CC)CC)C>[C:1]1([S:7]([CH2:19][C:18]2[CH2:17][C@@H:16]3[C@:14]([CH3:15])([CH2:32][CH:31]=[C:30]4[C@H:20]3[CH2:21][CH2:22][C:23]3[C@:28]4([CH3:29])[CH:27]=[CH:26][C:25](=[O:33])[CH:24]=3)[C:13]=2[C:10](=[O:12])[CH3:11])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

6

Edukt 3

HCID 1061PhosphateHCID 4190003Benzenesulfinyl chlorideHCID 1357883717beta-Hydroxy-16-methylenepregna-1,4,9(11)-triene-3,20-dione

Produkt 1

HCID 5718204716-(Phenylsulfinylmethyl)pregn-1,4,9(11),16-tetraene-3,20-dione

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittel2×
HCID 8471TriethylamineLösungsmittel

Versuchsvorschrift

Phenylsulfinyl chloride in methylene chloride (2.5N, 2.4 ml) was added to a mixture of 17α-acetyl-17β-hydroxy-16-methyleneandrost-1,4,9(11)-trien-3-one (VB, Example 17, 1 g) in methylene chloride (10 ml) and triethylamine (0.82 ml) previously cooled to -30° over a period of 2 hrs. The reaction is plunged into phosphate buffer (pH 7, 10 ml); the phases are separated; the aqueous phase is extracted with methylene chloride; the organic phases are combined and dried over sodium sulfate and concentrated under reduced presure to an isomeric mixture of the title compound. The isomers are separated by chromatography on silica gel (50 g), eluting with acetone/hexane: 5/95 to give the title compound, NMR (CDCl3) 0.89, 1.42, 2.10, 4.03, 5.5, 6.0, 6.27, 7.20 δ.

Aufarbeitung

  1. temperaturepreviously cooled to -30° over a period of 2 hrs
  2. customthe phases are separated
  3. extractionthe aqueous phase is extracted with methylene chloride
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated under reduced presure to an isomeric mixture of the title compound
  6. customThe isomers are separated by chromatography on silica gel (50 g)
  7. washeluting with acetone/hexane

Quellen und Nachweise

ORD-Eintrag
ord-f7977debaa2e407ebe39837cb647285f
Quelldatensatz
uspto-grants-1986_01
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US04567001

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