Reaktion #48895

ord-4a21139022934614aaca272b8999f93e

Reaktionsgleichung

C[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](OC(=O)C(F)(F)F)C[C@]2(C)[C@@]1(O)C(=O)CO
1-3
C[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](OC(=O)C(F)(F)F)C[C@]2(C)[C@@]1(O)C(=O)CO
(11β,16β)-9-fluoro-17,21-dihydroxy-16-methyl-3,20-dioxo-11-trifluoroacetoxy-pregna-1,4-diene
CC(=O)OC(C)=O
acetic anhydride
→
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](OC(=O)C(F)(F)F)C[C@@]21C
1-4
Ausbeute 94.7%
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](OC(=O)C(F)(F)F)C[C@@]21C
(11β,16β)-9-fluoro-17-hydroxy-16-methyl-3,20-dioxo-11-trifluoroacetoxy-21-acetoxy-pregna-1,4-diene
Ausbeute 94.7%

Edukte

C[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](OC(=O)C(F)(F)F)C[C@]2(C)[C@@]1(O)C(=O)CO
1-3
C[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](OC(=O)C(F)(F)F)C[C@]2(C)[C@@]1(O)C(=O)CO
(11β,16β)-9-fluoro-17,21-dihydroxy-16-methyl-3,20-dioxo-11-trifluoroacetoxy-pregna-1,4-diene
CC(=O)OC(C)=O
acetic anhydride

Reagenzien

CN(C)c1ccncc1
DMAP

Lösungsmittel

C1CCOC1
THF

Reaktionsbedingungen

Temperatur
35°CELSIUS
Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    SonstigeThe solvent was evaporated
  2. 2
    workup.ADDITIONthe residue diluted with 1 L of water
  3. 3
    SonstigeThe precipitate was isolated by filtration
  4. 4
    Sonstigedried for 15 hrs in

Vorschrift

To a solution of 1-3 (122.5 g) in THF (1 L) at RT was added DMAP (6.0 g, 49 mmol) and acetic anhydride (50.2 g, 491 mmol) and the mixture allowed to stir for 15 hours. The solvent was evaporated, and the residue diluted with 1 L of water. The precipitate was isolated by filtration and dried for 15 hrs in a warm (35° C.) vacuum oven to produce 123.4 g (94.7%) 1-4 as an off-white solid.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US07745657B2uspto-grants-2010_06