Reaktionsschritte
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).
