青蒿素生物合成的研究——Ⅱ.前体[15-~2H]-和[15-~3H]-青蒿酸的化学合成  

Studies on the Biosynthesis of Arteannuin Ⅱ.The Chemical Synthesis of the Precursors[15-~2H]-and[15-~3H]-Arteannuic Acid

作　　者：夏志强[1] 黄敬坚 汪猷[1] 

机构地区：[1]中国科学院上海有机化学研究所,上海200032

出　　处：《化学学报》1991年第12期1514-1518,共5页Acta Chimica Sinica

摘　　要：青蒿酸甲酯(5)用 NBS 溴化产生的溴化物,经 NaBD_3CN 或 NaBD_4氘解,生成[15-~2H]-青蒿酸甲酯(6),其结构由 MS,~1H,~2H 和^(13)C 的 NMR 确定.(6)经水解生成[15-~2H]-青蒿酸(4),用同样方法以 NaB^3H_4为氘化试剂与与溴化物反应,合成了[15-~3H]-青蒿酸(1).The bromination of methyl arteannuate(5)with NBS in CHCl_3 gave a mixture of6 with another monobromo-compound which was obtained by TLC and HPLC(yield:62%).The mixture was deuterized by NaBD_3CN or NaBD_4 in HMPA.From the product[15-H]-methyl arteannuate(6)was isolated and purified by TLC and HPLC(totalyield:13%).Its structure was determined by MS,and ~1H, ~2H and ^(13)C NMR.The ~1H NMRpeak of 15-H of 6 is lower than that of 5.The other peaks of 5 and 6 are same.The ^(13)CNMR spectrum difference between 5 and 6 is characterized by 15-C peak.The chemicalshift of peak of 6 is δ23.52(t)ppm,and,that of 5,23.72(q)ppm.The hydrolysis of 6gave[15-H]-arteannuic acid(4)[m.p.126—129℃,[α]_D^(20) 31.1°(c,0.01,CHCl_3);2:m.p.130℃,[α]_D^(28.5) 31.3(c,0.0093,CHCl_3)~[2]].[15-~3H]-arteannuic acid was alsosynthesized by the same method but using NaB^3H_4 instead of NaBD_4 as a tritiatingagent(radioactivity yield:12%;specific radioactivity:10~8 dpm/mg).

关 键 词：青蒿素 前体青蒿酸 合成 

分 类 号：R979.1[医药卫生—药品]