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四种太白山药用植物的化学成分研究
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摘要
本论文从天然产物化学的角度出发,以植物化学和现代化学分离技术为基础,对四种太白山药用植物的化学成分进行了系统研究。运用柱层析、重结晶等多种分离技术,借助现代波谱学技术(UV, IR, MS, 1D-NMR, 2D-NMR等),共分离鉴定了70余个化合物,包括2个新化合物:1个新木质素4'-(1'-propenoic methyl ester)phenoxyl caffeate和1个新呋喃螺旋甾烷皂苷(25S)-22,25-Epoxy-26-[(α-L-arabinopyranosyl)oxy]-3β-hydroxy- furost-5-en-1β-O-β-D-glucoside.主要研究结果如下:
     1.白果七,又名鸡爪七、天王七,系忍冬科莛子藨属植物莛子藨,主治劳伤、风湿腰腿痛、跌打损伤、消化不良、月经不调、白带等症。本文从其全草甲醇提取物中分离鉴定了12个化合物,分别为3个环烯醚萜苷裂马钱素二甲基乙缩醛(TZB-1),獐芽菜苷(TZB-4)和Vogeloside (TZB-13);2个黄酮类化合物木犀草素4'-O-β-D-葡萄糖苷(TZB-2)和华良姜素(TZB-3);2个香豆素类化合物嗪皮啶(TZB-6)和东莨菪内酯(TZB-7);3个三萜化合物乌苏酸(TZB-8), 3β-乙酰乌苏酸(TZB-9)和Hederagonic acid (TZB-10);2个苯丙酸衍生物咖啡酸甲酯(TZB-11)和绿原酸甲酯(TZB-12)。其中,化合物TZB-2, 3, 6, 7, 8, 9, 10, 11, 12等9个化合物为首次从该植物中分离得到。
     2.黑点草,又名黄瓜菜、大黄瓜香、瓜米菜,百合科油点草属植物黄花油点草的根或全草,主治口渴虚寒、狂躁不安、劳伤水肿等症。本文从其全草甲醇提取物中分离鉴定了16个化合物,分别为7个甾体化合物12α-羟基孕烯醇酮(HSQ-1),豆甾-4-烯-3-酮(HSQ-3),豆甾醇(HSQ-4),β-谷甾醇(HSQ-6),β-胡萝卜苷(HSQ-8), 5α-豆甾烷-3β,6α-二醇(HSQ-10)和孕烯醇酮(HSQ-11);6个黄酮类化合物阿福豆苷(HSQ-2),山奈酚(HSQ-13), 5,7,2′,6′-四羟基二氢黄酮(HSQ-14),烟花苷(HSQ-15),槲皮素(HSQ-16)和山奈酚3-O-β-D-葡萄糖苷-7-O-α-L-鼠李糖苷(HSQ-17);1个木质素4'-(1'-Propenoic methyl ester) phenoxyl caffeate (HSQ-7);以及2个小分子化合物邻苯二酚(HSQ-5)和原儿茶酸(HSQ-12)。以上化合物均为首次从该植物中分离得到;化合物HSQ-7为1个新的木质素类化合物。
     3.兔儿伞,别名一把伞、贴骨伞、雨伞菜、龙头七,菊科兔儿伞属植物兔儿伞的根或全草,主治风湿麻木、肢体疼痛、跌打损伤、月经不调、痛经、痈疽肿毒、痨疬、痔疮。本文从其全草甲醇提取物中分离鉴定了14个化合物,分别为8个黄酮类化合物槲皮苷(TES-1),异槲皮苷(TES-3),阿福豆苷(TES-4), 4′,7,8-三羟基异黄酮7-O-β-D-葡萄糖苷(TES-6),萹蓄苷(TES-8),大豆苷(TES-12),槲皮素(TES-13)和芒柄花苷(TES-14);1个芪类化合物(+)-α-Viniferin (TES-2);2个甾体化合物胡萝卜苷(TES-5a)和豆甾醇3-O-β-D-葡萄糖苷(TES-5b);2个三萜化合物齐墩果酸(TES-9)和4-表常春藤酸(TES-10);1个糖醇D-阿拉伯糖醇(TES-7)。其中,化合物TES-2, 4, 5a, 5b, 6, 7, 8, 9, 10, 12, 14等11个化合物为首次从该植物中分离得到。
     4.铁筷子,别名黑毛七、小桃儿七、鸳鸯七、九百棒,是毛茛科铁筷子属植物铁筷子的根茎,主治膀胱炎、尿道炎、疮疖肿毒、跌打损伤、劳伤等症。本文从其根茎70%乙醇提取物中分离鉴定了30个化合物,分别为7个蜕皮激素类化合物β-蜕皮激素(TGC-1), Polypodine B (TGC-2), 2,3-异丙叉基β-蜕皮激素(TGC-3),α-蜕皮激素(TGC-13),β-蜕皮激素3-O-β-D-葡萄糖苷(TGC-14), 3-乙酰基β-蜕皮激素(TGC-23)和5β-羟基蜕皮激素3-O-β-D-葡萄糖苷(TGC-37); 6个蟾蜍二烯内酯类化合物去乙酰蟾毒它灵(TGC-5),嚏根草配基(TGC-7), Deglucohellebrin (TGC-12),嚏根草因3-O-β-D-葡萄糖苷(TGC-15), Tigencaoside A (TGC-20)和Tigencaoside B (TGC-22);5个黄酮类化合物木犀草素4'-O-β-D-葡萄糖苷(TGC-8), Vincetoxicoside B (TGC-24),芦丁(TGC-25), 5-羟基-7-甲氧基二氢黄酮(TGC-30)和槲皮素(TGC-36);2个蒽醌类化合物大黄素甲醚(TGC-16)和大黄酚(TGC-18);2个芳基萘类木质素鬼臼毒素(TGC-19a)和苦鬼臼毒素(TGC-19b);1个呋喃螺旋甾烷皂苷(25S)-22,25-Epoxy-26-[(α-L-arabinopyranosyl)oxy]-3β- hydroxy-furost-5-en-1β-O-β-D-glucoside (TGC-4);以及其它化合物β-谷甾醇(TGC-21),葡萄糖(TGC-11),琥珀酸(TGC-29),香草酸(TGC-32), (3S,4R)-3-Hydroxy-4-hydroxy methyl-4-butanolide (TGC-33),对羟基苯甲酸(TGC-34)和藜芦酸(TGC-35)。其中,化合物TGC-3, 5, 8, 11, 13, 14, 16, 18, 19a, 19b, 21, 23, 24, 25, 29, 30, 32, 33, 34, 35, 36, 37等22个化合物为首次从该植物中分离得到;化合物TGC-4为1个新的呋喃螺旋甾烷皂苷。
Based on the theories of natural products chemistry and the modern chemical separation technology, the chemical constituents from four medicinal plants in Taibai mountain were studied. About 70 compounds, including two new compounds: a new lignan 4'-(1'-propenoic methyl ester)phenoxyl caffeate, a new furospirostanol saponin (25S)-22,25-Epoxy-26-[(α-L- arabinopyranosyl)oxy]-3β-hydroxy-furost-5-en-1β-O-β-D-glucoside. The results are concluded as follows:
     1. Bai Guo Qi, commonly named as“Ji Zhao Qi”or“Tian Wang Qi”, is the root or the whole plant of Triosteum pinnatifidum Maxim., belonging to the Triosteum genus of Caprifoliaceae family. It is used for the treatment of rheumatic disease, traumatic injury, dyspepsia and menoxenia. Twelve compounds were isolated from the methanolic extract of the whole plant of T. pinnatifidum, as three iridoid glycosides: Secologanin dimethylacetal (TZB-1), Sweroside (TZB-4) and Vogeloside (TZB-13); two flavonoids: Luteolin 4′-O-β-D-glucoside (TZB-2) and Kumatakenin (TZB-3); two coumarins: Fraxidin (TZB-6) and Scopoletin (TZB-7); three triterpenoids: Ursolic acid (TZB-8), 3β-O-Acetylursolic acid (TZB-9) and Hederagonic acid (TZB-10); two phenylpropanoids: Methyl caffeate (TZB-11) and Methyl chlorogenate (TZB-12). Among them, nine compounds TZB-2, 3, 6, 7, 8, 9, 10, 11, 12 were reported for the first time from this plant.
     2. Hei Dian Cao, locally known as“Huang Gua Cai”,“Da Huang Gua Xiang”or“Gua Mi Cai”, is the root or the whole plant of Tricyrtis maculata (D. Don) Machride, belonging to the family Liliaceae. It's a kind of Chinese medicinal herb, which is used for the treatment of gastric hot thirsty, restlessness and ministry oedema. Sixteen compounds were isolated from the methanolic extract of the whole plant of T. maculata, as seven steroids: 12α-Hydroxyprogesterone (HSQ-1), Stigmast-4-en-3-one (HSQ-3), Stigmasterol (HSQ-4),β-Sitosterol (HSQ-6),β-Daucosterol (HSQ-8), 5α-Stigmastane-3β,6α-diol (HSQ-10) and Pregnenolone (HSQ-11); six flavonoids: Afzelin (HSQ-2), Kaempferol (HSQ-13), 5,7,2′,6′-Tetrahydroxyflavone (HSQ-14), Nicotiflorin (HSQ-15), Quercetin (HSQ-16) and Kaempferol 3-O-β-D-gluco-pyranoside-7-O-α-L-rhamnopyranoside (HSQ-17); one lignan 4'-(1'-Propenoic methyl ester)phenoxyl caffeate (HSQ-7); two small molecules: Pyrocatechol (HSQ-5) and Protocatechuic acid (HSQ-12). They were reported for the first time from this plant, and the compound HSQ-7 is a new lignan.
     3. Tu'er San, locally known as“Yi Ba San”,“Yu San Cai”or“Long Tou Qi”, is the root or the whole plant of Syneilesis aconitifolia (Bge.) Maxim., belonging to the Syneilesis genus of Compositae family. It's used for the treatment of pain of arthritis, stomachalgia, menoxenia and hemorrhoids. Fourteen compounds were isolated from the methanolic extract of the whole plant of S. aconitifolia, as eight flavonoids: Quercitrin (TES-1), Isoquercitrin (TES-3), Afzelin (TES-4), 4′,7,8-Trihydroxy-isoflavone 7-O-β-D-glucopyranoside (TES-6), Avicularin (TES-8), Daidzin (TES-12), Quercetin (TES-13) and Ononin (TES-14); one stilbenoid: (+)-α-Viniferin (TES-2); two steroids: Daucosterol (TES-5a) and Stigmasterol 3-O-β-D- glucopyranoiside (TES-5b); two triterpenoids: Oleanic acid (TES-9) and 4-epi-Hederagenic acid (TES-10); one sugar alcohol: D-Arabinitol (TES-7). Among them, eleven compounds TES-2, 4, 5a, 5b, 6, 7, 8, 9, 10, 12, 14 were reported for the first time from this plant.
     4. Tie Kuai Zi, commonly named as“Hei Mao Qi”or“Xiao Tao Qi”, is Helleborus thibetanus Franch., belonging to the family Ranunculaceae. Its dried rhizomes have been used as Chinese folk medicine for the treatment of cystitis, urethritis and traumatic injury. Thirty compounds were isolated and purified from 70% ethanolic extract of the rhizomes of H. thibetanus, as seven phytoecdystones:β-Ecdysterone (TGC-1), Polypodine B (TGC-2),β-Ecdysterone 2,3-monoacetonide (TGC-3),α-Ecdysone (TGC-13),β-Ecdysterone 3-O-β-D- glucoside (TGC-14),β-Ecdysterone 3-acetate (TGC-23) and 5β-Hydroxyecdysone 3-O-β-D- glucoside (TGC-37); six bufadienolides:Desacetylbufotalin (TGC-5), Hellebrigenin (TGC-7), Deglucohellebrin (TGC-12), Hellebrigenin 3-O-β-D-glucoside (TGC-15), Tigencaoside A (TGC-20) and Tigencaoside B (TGC-22); five flavonoids: Luteolin 4′-O-β-D-glucoside (TGC-8), Vincetoxicoside B (TGC-24), Rutin (TGC-25), 5-Hydroxy-7-methoxyflavanone (TGC-30) and Quercetin (TGC-36); two anthraquinones: Physcion (TGC-16) and Chrysophanol (TGC-18); two arylnaphthalenes Podophyllotoxin (TGC-19a) and (-)-Picropodophyllotoxin (TGC-19b); one furospirostanol saponin (25S)-22,25-Epoxy- 26-[(α-L-arabinopyranosyl)oxy]-3β-hydroxy-furost-5-en-1β-O-β-D-glucoside (TGC-4); and other small molecules:β-Sitosterol (TGC-21), Glucose (TGC-11), Succinic acid (TGC-29), Vanillic acid (TGC-32), (3S,4R)-3-Hydroxy-4-hydroxymethyl-4-butanolide (TGC-33), p-Hydroxybenzoic acid (TGC-34) and Veratric acid (TGC-35). Among them, twenty-two compounds TGC-3, 5, 8, 11, 13, 14, 16, 18, 19a, 19b, 21, 23, 24, 25, 29, 30, 32, 33, 34, 35, 36, 37 were reported for the first time from this plant. The compound TGC-4 is a new furospirostanol saponin.
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