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化学学报
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化学学报 ›› 1991, Vol. 49 ›› Issue (12): 1514-1518. 上一篇    

研究论文

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

夏志强;黄敬坚;汪猷   

  1. 中国科学院上海有机化学研究所.上海(200032)
  • 发布日期:1991-12-15

Studies on the biosynthesis of arteannuin II. The chemical synthesis of the precursors [15-^2H]- and [15-^3H]-arteannuic acid

Xia Zhiqiang;Huang Jingjian;Wang You   

  1. Shanghai Inst Organ Chem., CAS.Shanghai(200032)
  • Published:1991-12-15

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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^1^3C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为氘化试剂与溴化物反应,合成了[15-^3H]-青蒿酸(1)。

关键词: 化学合成, 青蒿酸, 前体, 生物合成, 青蒿素, 核磁共振, 质谱法, 氘试剂, 溴化物, 水解

The bromination of methyl arteannuate (5) with NBS in CHCl~3 gave a mixture of 6 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 (total yield: 13%). Its structure was determined by MS, and ^1H, ^2H and ^1^3C NMR. The ^1H NMR peak of 15-H of 6 is lower than that of 5. The other peaks of 5 and 6 are same. The ^1^3C NMR spectrum difference between 5 and 6 is characterized by 15-C peak. The chemical shift of peak of 6 is δ is 23.52 (t)ppm, and, that of 5, 23.72(q)ppm. The hydrolysis of 6 gave [15-H]-arteannuic acid (4) [m.p. 126-129℃, [α]~D^2^0 31.1ⅲ (c, 0.01, CHCl~3); 2: m.p. 130℃, [α]~D^2^8^.^5 31.3 (c, 0.0093, CHCl~3)^[^2^]] . [15-^3H]-arteannuic acid was also synthesized by the same method but using NaB^3H~4 instead of NaBD~4 as a tritiating agent (radioactivity yield: 12%; specific radioactivity: 10^8 dpm/mg).

Key words: CHEMICAL SYNTHESIS, ARTEANNUIC ACID, PRECURSOR, BIOSYNTHESIS, ARTEANNUIN, NUCLEAR MAGNETIC RESONANCE, MASS SPECTROGRAPHY, DEUTERIUM REAGENTS, BROMIDE, HYDROLYSIS

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