Dimethyl Sulfoxide → Codeinone

HRID 362625

Reaktionsgleichung

Reaktionsgleichung von HRID 362625
CS(C)=O.C(Cl)(=O)C(Cl)=O.[CH3:11][N:12]1[C@@H:28]2[CH2:29][C:17]3[CH:18]=[CH:19][C:20]([O:31][CH3:32])=[C:21]4[O:22][C@H:23]5[C@@H:24]([OH:30])[CH:25]=[CH:26][C@@H:27]2[C@:15]5([C:16]=34)[CH2:14][CH2:13]1.CCN(CC)CC>C(Cl)Cl>[CH3:11][N:12]1[C@@H:28]2[CH2:29][C:17]3[CH:18]=[CH:19][C:20]([O:31][CH3:32])=[C:21]4[O:22][C@H:23]5[C:24]([CH:25]=[CH:26][C@@H:27]2[C@:15]5([C:16]=34)[CH2:14][CH2:13]1)=[O:30]

Komponenten

6

Edukt 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 5284371Codeine

Produkt 1

HCID 5459910CodeinoneAusbeute 126,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel4×

Versuchsvorschrift

To a solution of dimethylsulfoxide (16.53 g, 0.21 mole) in CH2Cl2 (80 ml) at -78° C. was added dropwise a solution of oxalyl chloride (13.01 g, 0.10 mole) in CH2Cl2 (50 ml) over a period of 40 min. After stirring for 10 min., a solution of codeine (20.33 g, 0.068 mole) in CH2Cl2 (100 ml) was added over 50 min. while keeping the reaction mixture at -78° C. After stirring at -78° C. for 2 hr., Et3N (50 ml) was added, followed by CH2Cl2 (100 ml). The reaction mixture was allowed to warm-up to room temperature, washed with water (6×150 ml), dried over anhydrous Na2SO4 and evaporated to dryness in vacuo to give codeinone (25.57 g). IR (KBr)(ν, cm-1): 1668 (s, sharp, --C=C--C=O); NMR (δH)(CDCl3): 6.67 (1, d, J, 8.2, 2-H), 6.62 (1, d, J, 10.2, 8-H), 6.59 (1, d, J, 8.2, 1-H), 6.07 (1, dd, J, 10.2 & 2.9, 7-H), 4.68 (1, s, 5-H), 3.85 (3, s, OCH3), 3.45-3.35 (1, m, 9-H), 3.25-3.17 (1, m, 14-H), 3.10 (1, d, J, 18.5, 10-Hβ), 2.61 (1, dm, J, 11.9, 16-He), 2.45 (3, s, NCH3), 2.30 (1, dd, J, 18.5 & 5.5, 10-Hα), 2.30 (1, td, J, 11.9 & 3.7, 16-Ha), 206 (1, td, J, 12.0 & 4.8, 15-Ha), 1.85 (1, dm, J, 12.5, 15-He).

Aufarbeitung

  1. customat -78° C
  2. stirringAfter stirring at -78° C. for 2 hr
  3. washwashed with water (6×150 ml)
  4. dry with materialdried over anhydrous Na2SO4
  5. customevaporated to dryness in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-59c214a6b542474ab7b8047e70754dbe
Quelldatensatz
uspto-grants-1999_02
Patentnummer
US05869669

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