Trifluoroacetic acid → 21-Hydroxy-17-(1-oxobutoxy)pregna-4,9(11)-diene-3,20-dione

HRID 1502626

Reaktionsgleichung

Reaktionsgleichung von HRID 1502626
[OH:1][C@:2]1([C@:23]2([CH3:24])[C@H:9]([C@H:10]3[C:20](=[CH:21][CH2:22]2)[C@:18]2([CH3:19])[C:13](=[CH:14][C:15](=[O:25])[CH2:16][CH2:17]2)[CH2:12][CH2:11]3)[CH2:8][CH2:7]1)[C:3](=[O:6])[CH2:4][OH:5].F[C:27](F)(F)[C:28]([OH:30])=O.O1CCO[CH2:35][CH2:34]1>C([O-])([O-])(OCC)CCC>[C:28]([O:1][C@:2]1([C@:23]2([CH3:24])[C@H:9]([C@H:10]3[C:20](=[CH:21][CH2:22]2)[C@:18]2([CH3:19])[C:13](=[CH:14][C:15](=[O:25])[CH2:16][CH2:17]2)[CH2:12][CH2:11]3)[CH2:8][CH2:7]1)[C:3](=[O:6])[CH2:4][OH:5])(=[O:30])[CH2:27][CH2:34][CH3:35]

Komponenten

5

Edukt 3

HCID 6422Trifluoroacetic acidHCID 312751,4-DioxaneHCID 7074810Anecortave

Produkt 1

HCID 1170435221-Hydroxy-17-(1-oxobutoxy)pregna-4,9(11)-diene-3,20-dione

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 865847631-Ethoxybutane-1,1-diolateLösungsmittel

Reaktionsbedingungen

Temperatur
45 °C

Versuchsvorschrift

4 g (11.6 mM) of 17a,21-dihydroxy-pregna-4,9(11)-diene-3,20-dione were reacted with 20 mg of trifluoroacetic acid in 20 ml of dioxane and 10 ml of ethyl orthobutyrate for 5 hours at 100° C., and the low boiling head fraction was distilled off. The solution was cooled, then treated with 5 ml of a tartaric acid molar solution and heated to 40-50° C. for about 5 minutes to obtain 17α-butanoyloxy-21-hydroxy-pregna-4,9(11)-diene-3,20-dione. The solvent was evaporated off under vacuum and the residue was repeatedly taken up with dioxane. The resulting residue was dissolved in 200 ml of acetone and then 12 g trifluoroethyl octadecanoate (prepared from octadecanoyl chloride and trifluoroethanol), 20 g of Candida cylindracea lipase were added and the resulting suspension was stirred for 8-10 hours at 50° C., adding 2 g of C. cylindracea at regular time intervals. The lipase was filtered off, the filtrate was concentrated under vacuum and the residue was chromatographed on a silica gel column with a dichloromethane/methanol 98.5:1.5 mixture. The neat fraction was evaporated to obtain 4.9 g (7.17 mM) of 17α-butanoyloxy-21-octadecanoyloxy-pregna-4,9(11)-diene-3,20-dione.

Aufarbeitung

  1. distillationthe low boiling head fraction was distilled off
  2. temperatureThe solution was cooled
  3. additiontreated with 5 ml of a tartaric acid molar solution

Quellen und Nachweise

ORD-Eintrag
ord-51c77fa1b33a430ab0ddd80c82df5b24
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09211295B2

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