药用植物花木蓝根的化学成分研究
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摘要
豆科木蓝属(Indigofera)植物在世界上约有700种,广泛分布于热带及亚热带地区。中国有80种8变种,主产于我国南部和西南部。该属多种植物的根在我国不少地区被长期作为传统中药山豆根的代用品,俗称“木蓝山豆根”,具有清热解毒、清咽利喉之效。但有文献报道部分病人在服用木蓝山豆根后出现以神经系统为主的中毒症状。
本论文对木蓝山豆根的主要来源植物之一——花木蓝(I. kirilowii Maxim. Ex Palibin)根的化学成分进行了系统研究,实验采用溶剂萃取、硅胶柱层析、大孔吸附树脂柱层析、重结晶等手段,从花木蓝根的乙醇提取物中分离得到18个化合物,并通过1H-NMR、13C-NMR、DEPT、COSY、HSQC、HMBC、MS等现代波谱技术分析及与标准品对照的方法,鉴定了其中16个的结构,它们分别是:亚油酸乙酯(IKrS-1)、亚油酸谷甾醇酯(IKrS-3)、咖啡酸长链脂肪醇酯(IKrS-4)、羽扇豆醇(IKrS-5)、谷甾醇(IKrS-6)、白桦脂酸(IKrS-7)、1-棕榈酸单甘油酯(IKrS-8)、乙酰齐墩果酸(IKrS-9)、6-氧-(3-硝基丙酰基)-α,β-D-吡喃葡萄糖(IKrE-11)、4′-甲氧基异黄酮-7-氧-β-D-葡萄糖苷(IKrE-12)、3,4-二-氧-(3-硝基丙酰基)-α,β-D-吡喃葡萄糖(IKrE-13)、3-硝基丙酸(IKrB30-1)、2,6-二-氧-(3-硝基丙酰基)-α-D-吡喃葡萄糖(IKrB30-2)、丁香酸葡萄糖苷(IKrB30-3)、2,3,6-三-氧-(3-硝基丙酰基)-α-D-吡喃葡萄糖(IKrB50-1)、橙皮苷(IKrB50-2)。以上化合物中,IKrE-13为新化合物,IKrS-1、IKrS-3、IKrS-4、IKrS-8、IKrS-9、IKrE-12和IKrB50-2均为首次从木蓝属植物中分离得到,IKrE-11为首次从花木蓝中分离得到。1H-NMR数据显示IKrS-2为正构长链脂肪酸,IKrB70-1初步鉴定为齐墩果烷型三萜皂苷,具体结构有待于进一步研究,但之前未见木蓝属中有三萜皂苷类成分的报道。化合物IKrE-11、IKrE-13、IKrB30-1、IKrB30-2和IKrB50-1可能为引起花木蓝根毒性的成分。
本文还对木蓝属植物的资源、化学成分、生物活性等的研究进展进行了综述;并对3-硝基丙酰基类化合物的结构特征、理化性质、波谱规律等作出了总结。
The genus Indigofera comprises about 700 species widely distributed in the tropical and subtropical regions of the world, and in China it is represented by 80 species. The roots of several Indigofera species are used as substitutes for traditional Chinese medicine“ShanDouGen”(Sophora tonkinensis Gapnep.) in many provinces of China. They are most commonly used in the treatment of inflammatory diseases, especially sore throat, while it has also been reported that some patients exhibited neural poisoning symptoms after taking high dosages.
In this thesis, we studied the chemical constituents of the roots of I. Kirilowii, which is one of the main resources of so-called“MuLanShanDouGen”. Eighteen compounds were isolated and purified from the alcohol extracts by solvent extraction, silica gel column chromatography, macroporous resin column chromatography and re-crystallization. On the basis of various modern spectral analysis and classical chemical methods, the structures of sixteen compounds were elucidated as ethyl linoleate (IKrS-1), sitosterol linoleate (IKrS-3), long-chain n-alkyl caffeate (IKrS-4), lupeol (IKrS-5), sitosterol (IKrS-6), betulinic acid (IKrS-7), 1-monopalmitin (IKrS-8), 3-acetyloleanolic acid (IKrS-9), 6-O-(3-nitropropanoyl)-α,β-D-glucopyranose (IKrE-11), Ononin (IKrE-12), 3,4-di-O-(3-nitropropanoyl)-α,β-D-glucopyranose (IKrE-13), 3-nitropropanoyl acid (IKrB30-1), 2,6-di-O-(3-nitropropanoyl)-α-D- glucopyranose (IKrB30-2), glucosyringic acid (IKrB30-3), 2,3,6-tri-O-(3- nitropropanoyl)-α-D-glucopyranose (IKrB50-1), hesperidin (IKrB50-2). Among these compounds, IKrE-13 is a new natural product, IKrS-1, IKrS-3, IKrS-4, IKrS-8, IKrS-9, IKrE-11, IKrE-12 and IKrB50-2 were isolated From the title plant for the first time. IKrS-2 is one of the long-chain aliphatic acids, and IKrB70-1 is being identified. IKrE-11, IKrE-13, IKrB30-1, IKrB30-2 and IKrB50-1 could be responsible for the toxicity of the roots of I. kirilowii.
We also summarized the studies on chemical constituents and bioactivities of Indigofera. Meanwhile, the characteristics of 3-nitropropanoyl glucopyranoses were summarized, too.
本论文对木蓝山豆根的主要来源植物之一——花木蓝(I. kirilowii Maxim. Ex Palibin)根的化学成分进行了系统研究,实验采用溶剂萃取、硅胶柱层析、大孔吸附树脂柱层析、重结晶等手段,从花木蓝根的乙醇提取物中分离得到18个化合物,并通过1H-NMR、13C-NMR、DEPT、COSY、HSQC、HMBC、MS等现代波谱技术分析及与标准品对照的方法,鉴定了其中16个的结构,它们分别是:亚油酸乙酯(IKrS-1)、亚油酸谷甾醇酯(IKrS-3)、咖啡酸长链脂肪醇酯(IKrS-4)、羽扇豆醇(IKrS-5)、谷甾醇(IKrS-6)、白桦脂酸(IKrS-7)、1-棕榈酸单甘油酯(IKrS-8)、乙酰齐墩果酸(IKrS-9)、6-氧-(3-硝基丙酰基)-α,β-D-吡喃葡萄糖(IKrE-11)、4′-甲氧基异黄酮-7-氧-β-D-葡萄糖苷(IKrE-12)、3,4-二-氧-(3-硝基丙酰基)-α,β-D-吡喃葡萄糖(IKrE-13)、3-硝基丙酸(IKrB30-1)、2,6-二-氧-(3-硝基丙酰基)-α-D-吡喃葡萄糖(IKrB30-2)、丁香酸葡萄糖苷(IKrB30-3)、2,3,6-三-氧-(3-硝基丙酰基)-α-D-吡喃葡萄糖(IKrB50-1)、橙皮苷(IKrB50-2)。以上化合物中,IKrE-13为新化合物,IKrS-1、IKrS-3、IKrS-4、IKrS-8、IKrS-9、IKrE-12和IKrB50-2均为首次从木蓝属植物中分离得到,IKrE-11为首次从花木蓝中分离得到。1H-NMR数据显示IKrS-2为正构长链脂肪酸,IKrB70-1初步鉴定为齐墩果烷型三萜皂苷,具体结构有待于进一步研究,但之前未见木蓝属中有三萜皂苷类成分的报道。化合物IKrE-11、IKrE-13、IKrB30-1、IKrB30-2和IKrB50-1可能为引起花木蓝根毒性的成分。
本文还对木蓝属植物的资源、化学成分、生物活性等的研究进展进行了综述;并对3-硝基丙酰基类化合物的结构特征、理化性质、波谱规律等作出了总结。
The genus Indigofera comprises about 700 species widely distributed in the tropical and subtropical regions of the world, and in China it is represented by 80 species. The roots of several Indigofera species are used as substitutes for traditional Chinese medicine“ShanDouGen”(Sophora tonkinensis Gapnep.) in many provinces of China. They are most commonly used in the treatment of inflammatory diseases, especially sore throat, while it has also been reported that some patients exhibited neural poisoning symptoms after taking high dosages.
In this thesis, we studied the chemical constituents of the roots of I. Kirilowii, which is one of the main resources of so-called“MuLanShanDouGen”. Eighteen compounds were isolated and purified from the alcohol extracts by solvent extraction, silica gel column chromatography, macroporous resin column chromatography and re-crystallization. On the basis of various modern spectral analysis and classical chemical methods, the structures of sixteen compounds were elucidated as ethyl linoleate (IKrS-1), sitosterol linoleate (IKrS-3), long-chain n-alkyl caffeate (IKrS-4), lupeol (IKrS-5), sitosterol (IKrS-6), betulinic acid (IKrS-7), 1-monopalmitin (IKrS-8), 3-acetyloleanolic acid (IKrS-9), 6-O-(3-nitropropanoyl)-α,β-D-glucopyranose (IKrE-11), Ononin (IKrE-12), 3,4-di-O-(3-nitropropanoyl)-α,β-D-glucopyranose (IKrE-13), 3-nitropropanoyl acid (IKrB30-1), 2,6-di-O-(3-nitropropanoyl)-α-D- glucopyranose (IKrB30-2), glucosyringic acid (IKrB30-3), 2,3,6-tri-O-(3- nitropropanoyl)-α-D-glucopyranose (IKrB50-1), hesperidin (IKrB50-2). Among these compounds, IKrE-13 is a new natural product, IKrS-1, IKrS-3, IKrS-4, IKrS-8, IKrS-9, IKrE-11, IKrE-12 and IKrB50-2 were isolated From the title plant for the first time. IKrS-2 is one of the long-chain aliphatic acids, and IKrB70-1 is being identified. IKrE-11, IKrE-13, IKrB30-1, IKrB30-2 and IKrB50-1 could be responsible for the toxicity of the roots of I. kirilowii.
We also summarized the studies on chemical constituents and bioactivities of Indigofera. Meanwhile, the characteristics of 3-nitropropanoyl glucopyranoses were summarized, too.
引文
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