Reaktion #935626

ord-85611ac782b447efa27f406ef50639c5

Reaktionsgleichung

CC(=O)[C@@]1(O)CC[C@H]2[C@@H]3C=C(Cl)C4=CC(=O)[C@@H]5C[C@@H]5[C@]4(C)[C@H]3CC[C@@]21C
6-chloro-17-hydroxy-1α,2α-methylene-4,6-pregnadiene-3,20-dione
II
iodine
[Ca+2].[O-2]
calcium oxide
II
iodine
C[C@@]12C(=CC(=O)[C@@H]3C[C@@H]31)C(Cl)=C[C@@H]1[C@@H]2CC[C@@]2(C)[C@H]1CC[C@]2(O)C(=O)CI
6-chloro-17-hydroxy-21-iodo-1α,2α-methylene-4,6-pregnadiene-3,20-dione
→
CC(=O)OCC(=O)[C@@]1(O)CC[C@H]2[C@@H]3C=C(Cl)C4=CC(=O)[C@@H]5C[C@@H]5[C@]4(C)[C@H]3CC[C@@]21C
21-acetoxy-6-chloro-17-hydroxy-1α,2α-methylene-4,6-pregnadiene-3,20-dione

Edukte

CC(=O)[C@@]1(O)CC[C@H]2[C@@H]3C=C(Cl)C4=CC(=O)[C@@H]5C[C@@H]5[C@]4(C)[C@H]3CC[C@@]21C
6-chloro-17-hydroxy-1α,2α-methylene-4,6-pregnadiene-3,20-dione
II
iodine
—
solution
—
ice water
[Ca+2].[O-2]
calcium oxide
—
azoisobutyronitrile
II
iodine
C[C@@]12C(=CC(=O)[C@@H]3C[C@@H]31)C(Cl)=C[C@@H]1[C@@H]2CC[C@@]2(C)[C@H]1CC[C@]2(O)C(=O)CI
6-chloro-17-hydroxy-21-iodo-1α,2α-methylene-4,6-pregnadiene-3,20-dione

Reagenzien

Keine

Lösungsmittel

CO
methanol
CCN(CC)CC
triethylamine
C1CCOC1
tetrahydrofuran
CC(C)=O
acetone
CC(=O)O
acetic acid
CO
methanol
C1CCOC1
tetrahydrofuran

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    SonstigeAfter an induction time of 60 minutes
  2. 2
    workup.ADDITIONThe reaction mixture is diluted with 500 ml
  3. 3
    Filtrationof dichloromethane, the calcium oxide is filtered off
  4. 4
    Waschenthe filtrate is washed with sodium thiosulfate solution and water
  5. 5
    Trocknendried over sodium sulfate
  6. 6
    Einengenconcentrated under vacuum at 35° C.
  7. 7
    Sonstigethus obtaining 13 g
  8. 8
    workup.DISSOLUTIONThis product is dissolved in 130 ml
  9. 9
    SonstigeThe thus-obtained precipitate is isolated
  10. 10
    Sonstigechromatographed on silica gel

Vorschrift

A solution of 10 g. of 6-chloro-17-hydroxy-1α,2α-methylene-4,6-pregnadiene-3,20-dione in 75 ml. of methanol and 75 ml. of tetrahydrofuran is combined with 15 g. of calcium oxide and 500 mg. of azoisobutyronitrile. Several milliliters of a solution of 10 g. of iodine in 50 ml. of tetrahydrofuran and 30 ml. of methanol are added dropwise to the reaction mixture. After an induction time of 60 minutes, the solution loses its color; the residual iodine solution is added dropwise within 8 hours. The reaction mixture is diluted with 500 ml. of dichloromethane, the calcium oxide is filtered off, and the filtrate is washed with sodium thiosulfate solution and water, dried over sodium sulfate, and concentrated under vacuum at 35° C., thus obtaining 13 g. of 6-chloro-17-hydroxy-21-iodo-1α,2α-methylene-4,6-pregnadiene-3,20-dione. This product is dissolved in 130 ml. of acetone and 45 ml. of acetic acid, combined with 69 ml. of triethylamine, and refluxed for 90 minutes. The solution is stirred into ice water. The thus-obtained precipitate is isolated and chromatographed on silica gel. With 16-20% acetone-pentane, 6.1 g. of 21-acetoxy-6-chloro-17-hydroxy-1α,2α-methylene-4,6-pregnadiene-3,20-dione is obtained, m.p. 224° C.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US04296109uspto-grants-1981_10