Osei-Gyimah P, Archer S
J Med Chem. 1980 Feb;23(2):162-6. doi: 10.1021/jm00176a011.
Treatment of 14 beta-nitrocodeinone with sodium borohydride gave the codeine derivative which was reduced with zinc dust in acetic anhydride-acetic acid solution to give 14 beta-acetamidocodeine 6-acetate. 14 beta-Thiocyanatocodeinone was obtained from the reaction of thebaine with thiocyanogen and was reduced to 14 beta-mercaptocodeine with lithium aluminum hydride. 14 beta-Bromo- and 14 beta-chlorocodeinone were prepared by the reaction of thebaine with N-bromosuccinimide and N-chlorosuccinimide, respectively. These 14 beta-substituted codeine and codeinones were O-demethylated to the corresponding morphine analogues with boron tribromide. With the exception of 14 beta-nitromorphinone, which was weak in activity, all the other 14 beta-substituted morphine derivatives were approximately equal in potency to normorphine in the guinea pig ileum preparation.
用硼氢化钠处理14β-硝基可待因酮得到可待因衍生物，该衍生物在乙酸酐 - 乙酸溶液中用锌粉还原得到14β-乙酰氨基可待因6 - 乙酸酯。14β-硫氰酸可待因酮由蒂巴因与硫氰生成反应制得，并用氢化铝锂还原为14β-巯基可待因。14β-溴代和14β-氯代可待因酮分别由蒂巴因与N - 溴代琥珀酰亚胺和N - 氯代琥珀酰亚胺反应制备。这些14β-取代的可待因和可待因酮用三溴化硼进行O - 去甲基化反应生成相应的吗啡类似物。除活性较弱的14β-硝基吗啡酮外，所有其他14β-取代的吗啡衍生物在豚鼠回肠制备实验中的效力与去甲吗啡大致相当。
