Reaktion #42652

ord-a6663e1989114dada27ab5d109dc064c

Reaktionsgleichung

CCCCCC.COC(C)(C)C.ClC(Cl)Cl
t-butyl methyl ether hexane chloroform
CC(=O)OCC(=O)[C@@]1(O)[C@@H](C)C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](O[Si](C)(C)C)C[C@@]21C
(11β,16β)-9-fluoro-17-hydroxy-16-methyl-3,20-dioxo-11-[(trimethyl-silyl)oxy]-pregna-1,4-dien-21-yl acetate
CCN=C=O
ethyl isocyanate
→
CCNC(=O)O[C@]1(C(=O)COC(C)=O)[C@@H](C)C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](O[Si](C)(C)C)C[C@@]21C
title compound
Ausbeute 62.5%
CCNC(=O)O[C@]1(C(=O)COC(C)=O)[C@@H](C)C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](O[Si](C)(C)C)C[C@@]21C
(11β,16β)-21-(acetyloxy)-9-fluoro-16-methyl-3,20-dioxo-11-[(trimethylsilyl)-oxy]pregna-1,4-dien-17-yl ethylcarbamate
Ausbeute 62.5%

Edukte

CCCCCC.COC(C)(C)C.ClC(Cl)Cl
t-butyl methyl ether hexane chloroform
CC(=O)OCC(=O)[C@@]1(O)[C@@H](C)C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](O[Si](C)(C)C)C[C@@]21C
(11β,16β)-9-fluoro-17-hydroxy-16-methyl-3,20-dioxo-11-[(trimethyl-silyl)oxy]-pregna-1,4-dien-21-yl acetate
CCN=C=O
ethyl isocyanate

Reagenzien

Keine

Lösungsmittel

Cc1ccccc1
toluene

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Temperaturthe mixture was refluxed for 48 hours
  2. 2
    Sonstigeevaporated under vacuum
  3. 3
    Sonstigeto leave a slightly gummy solid

Vorschrift

To a mixture of (11β,16β)-9-fluoro-17-hydroxy-16-methyl-3,20-dioxo-11-[(trimethyl-silyl)oxy]-pregna-1,4-dien-21-yl acetate (3.11 g, 6.15 mmol) in 41 mL of toluene was added neat ethyl isocyanate (20.5 mL, 259 mmol) and the mixture was refluxed for 48 hours. The resulting solution was cooled to room temperature and evaporated under vacuum to leave a slightly gummy solid. Flash chromatography through a 1 kg column of silica gel eluting with t-butyl methyl ether/hexane/chloroform (1:1:1) gave 2.22 g of the title compound as a white solid.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US07732432B2uspto-grants-2010_06