朱砂根和密花石豆兰活性成分的研究
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摘要
本文使用稻瘟霉活性筛选模型(Pyricularia oryzae bioassay)和肿瘤细胞体外活性测试方法(MTT法)对紫金牛属植物朱砂根(Ardisia crenata Sims)和石豆兰属植物密花石豆兰(Bulbophillum odoratissimum Lindl.)进行了活性化合物的追踪分离及结构鉴定工作。
     利用现代色谱手段从朱砂根的干燥根茎中分离得到24个化合物,通过化学和光谱学方法鉴定了它们的结构,它们分别是:岩白菜素bergenin(1),朱砂根皂苷Iardisicrenoside I(2)~*,朱砂根皂苷J ardisicrenoside J(3)~*,朱砂根皂苷K ardisicrenoside K(4)~*,百两金皂苷A ardisiacrispin A(5),百两金皂苷B ardisiacrispin B(6),朱砂根皂苷B ardisicrenoside B(7),朱砂根皂苷A ardisicrenoside A(8),朱砂根皂苷D ardisicrenoside
     D(9),朱砂根皂苷M ardisicrenoside M(10)~*,朱砂根皂苷C ardisicrenoside C(11),朱砂根皂苷L ardisicrenoside L(12)~*,朱砂根皂苷H ardisicrenoside H(13),朱砂根皂苷G
     ardisicrenoside G(14),3β-O-{β-D-木吡喃糖基-(1→2)-β-D-葡萄吡喃糖基-(1→4)-[β-D-葡萄吡喃糖基-(1→2)]-α-L-阿拉伯吡喃糖基}-16α,28-二羟基-齐墩果-12-烯-30-醛3β-O-{β-D-xylopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→2)]-α-L-arabinopyranosyl}-16α,28-dibydroxy-olean-12-en-30-aldehydc(15),3β,16α-二羟基-30-甲氧基-28,30-环氧-齐墩果-12-烯 3β,16α-dihydroxy-30-methoxy-28,30-epoxy-olean-12-en(16),2,4,6-三羟基苯甲酸2,4,6-tribydroxybenzoic acid(17),朱砂根皂苷P ardisicrenoside P(18)~*,西克拉明皂苷元A-3β-O-β-D-葡萄吡喃糖基-(1→2)-α-L-阿拉伯吡喃糖苷cyclamiretin A-3β-O-β-D-glucopyranosyl-(1→2)-α-L-arabinopyranoside(19),西克拉明皂苷元A-3β-O-β-D-葡萄吡喃糖基-(1→4)-α-L-阿拉伯吡喃糖苷cyclamiretin A-3β-O-β-D-glucopyranosyl-(1→4)-α-L-arabinopyranoside(20),西克拉明皂苷元A-3β-O-β-D-木吡喃糖基-(1→2)-β-D-葡萄吡喃糖基-(1→4)-α-L-阿拉伯吡喃糖苷cyclamiretin A-3β-O-β-D-xylopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)-α-L-arabinopyranoside(21),西克拉明皂苷元A-3β-O-α-L-鼠李吡喃糖基-(1→2)-β-D-葡萄吡喃糖基-(1→4)-α-L-阿拉伯吡喃糖苷cyclamiretin A-3β-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)-α-L-arabinopyranoside(22),朱砂根皂苷N ardisicrenoside N(23)~*,朱砂根皂苷O ardisicrenoside O(24)~*。这24个化合物中,化合物16为三萜皂苷元类化合物,化合物1和17为小分子化合物,其余的21个化合物均为五环三萜皂苷类化合物。其中化合物2,3,4,10,12,18,23,24为新化合物,化合物15-17,19-22为首次
    
    沈阳药科大学体士学位论文
    摘县
    云百百百面面.面面面困面口口面万
    从该属植物中分离得到。
     利用现代色谱手段从密花石豆兰的干燥全草中分离得到29个化合物,通过化学和
    光谱学方法鉴定了它们的结构,分别是:2,2,一二轻基一3,3‘一二甲氧基一4,5一亚甲二氧基二
    节(2,2‘一dihydz·oxy一3,3‘一dimethoxy一4,5一methylenedioxybibenzyl)(1)*,3,一轻基·3,5‘一二甲氧
    基一4,5一亚甲一二氧基二节(3’·hydroxy一3,5‘一 dimethoxy一4,5一ethylenedioxybibenzyl)(2)*,
    2,3,一二经基一3一甲氧基一4,5一亚甲二氧基二节(2,3,一diliydroxy·3-methoxy-4,
    5一methyleoedioxybibenzyl)(3),3‘,3一二经基一4,5一亚甲二氧基二节(3’,3·dihydroxy-4,
    5一methylened互oxybibenzyl)(4),3‘一经基一3一甲氧基一4,5一亚甲二氧基二节
    (3’一勿droxy一3一methoxy一4,5一methylenediox沙ibenZyl)(5),2一轻基一5一甲氧基一3,4,3‘,4’一二
    亚甲二氧基二节(2一hy由oxy一5一methoxy·3,4,3‘,4‘一dimethylenedioxybibenZyl)(6),5‘一经基
    一5一甲氧基一2,2‘一氧骄一3,4一亚甲二氧基二节(弘坤droxy一5一methoxy一2,2’·。抑in-3,4-
    methylenedioxybibenzyl)(7),4,5‘一二经基一3,3’一二甲氧基二节(4,5‘一dihydro材·3,
    3’一dimethox乃七ibenzyl)(s),4,5‘一二轻基一3,3’,5一三甲氧基二节(4,5‘·diliydroxy一3,3‘,
    5一trimethoxybibenzyl)(9),3,3‘一二经基一5‘一甲氧基二节(batatasin 111)(10),3‘一轻基一3,5-
    二甲氧基二节(3’一妙droxy一3,5一dimethoxybibenZyl)(11),2气(3“,5气二甲氧基一4即一经基苯
    基升3’一经基一2‘,3‘一二氢一4H-毗喃[5,,6‘一112一经基·5一甲氧基菲[2‘一(3“,
    5“一dimethoxy·4,‘一hydro郑benzyl)一3‘一hydroxy一2‘,3‘一dihydrO.4H-pyrano[5‘,6‘一习2一drO材-
    5一methox即henanthrene](12)*,2,7一二轻基一3,4一二甲氧基菲(2,7·dlhydroxy一3,
    4一dimethox),henanthrene)(13),2,5·二轻基一3,4一二甲氧基菲(2,5·dihydroxy·3,
    4一dimethox),henant脉ne)(14),2,7一二轻基·4一甲氧基菲(2,
    7一dihydro:
In this dissertation, the Pyricularia oryzae bioassay was used to search anticancer compounds, 24 compounds were obtained from Ardisia crenata Sims and 29 compounds were obtained from Bulbophyllum odoratissimum Lindl.. Their structures were elucidated on the basis of chemical evidences and spectral analysis.
    The 24 compounds from A. crenata Suns are bergenin (1), ardisicrenoside I (2)*, ardisicrenoside J (3)*, ardisicrenoside K (4)*, ardisiacrispin A (5), ardisiacrispin B (6), ardisicrenoside B (7), ardisicrenoside A (8), ardisicrenoside D (9), ardisicrenoside M (10)*, ardisicrenoside C (11), ardisicrenoside L (12)*, ardisicrenoside H (13), ardisicrenoside G (14), 3B-0-{p-D-xylopyranosyl-(1- 2)-B-D-glucopyranosyl-(l - 4)-[(B-D-glucopyranosyl-(l -2)]-a-L-arabinopyranosyl}-16a, 28-dihydroxy-olean-12-en-30-aldehyde(15), 3p, 16a-dihydroxy-30-methoxy-28, 30-epoxy-olean-12-en (16), 2, 4, 6-trihydroxybenzoic acid (17), ardisicrenoside P (18)*, 3p-0-[p-D-glucopyranosyl-(l -* 2)-a-L-arabinopyranosyl] cyclamiretin A(19), 3p-O-[p-D-glucopyranosyl-(1-4)-a-L-arabuiopyranosyl] cyclamiretin A(20), 3B-0-[B-D-xylopyranosyl-(l -2)-p-D-glucopyranosyl-(1-4)-a-L-arabinopyranosyl] cyclamiretin A(21), 3B-0-[a-L-rhamnopyranosyl-(1 - 2)-B-D-glucopyranosyl-(1 - 4) -a-L-arabinopyranosyl] cyclamiretin A (22), ardisicrenoside N (23) *, ardi
    sicrenoside 0 (24) *, respectively. Compound 2, 3, 4,10,12,18,23 and 24 are new, compound 15-17 and 19-22 were isolated for the first time from Ardisia genus.
    The 29 compounds from Bulbophyllum odoratissimum Lindl. are 2, 2'-dihydroxy-3, 3'-dimethoxy-4, 5-methylenedioxybibenzyl (1)*, 3'-hydroxy-3, 5'-dimethoxy-4, 5-methylenedioxybibenzyl (2)*, 2, 3'-dihydroxy-3-methoxy-4, 5-methylenedioxybibenzyl (3), 3', 3-dihydroxy-4, 5-methylenedioxybibenzyl (4), 3'-hydroxy-3-methoxy-4, 5-methylenedioxybibenzyl (5), 2-hydroxy-5-methoxy-3, 4, 3', 4'-dimethylenedioxybibenzyl (6), 5'-hydroxy-5-methoxy-2, 2'-oxrpin-3, 4-methylenedioxybibenzyl (7), 4, 5'-dihydroxy-3, 3'-dimethoxybibenzyl (8), 4, 5'-dihydroxy-3, 3', 5-trimethoxybibenzyl (9), batatasin III(10), 3'-hydroxy-3, 5-dimethoxybibenzyl (11), 2'-(3", 5"-dunethoxy-4"-hydroxybenzyl)-3'-hydroxy-2', 3'-dihydro-4H-pyrano [5', 6'-i]2-hydroxy-5-methoxyphenanthrene (12)*, 2,
    
    
    7-dihydroxy-3, 4-dimethoxyphenanthrene(13), 2, 5-dihydroxy-3, 4-dimethoxyphenanthrene (14), 2, 7-dihydroxy-4-methoxyphenanthrene (IS), 2, 7-dihydroxy-3, 4-dimethoxy-9, 10-dihydrophenanthrene(16), 2, 7-dihydroxy-4-methoxy-9, 10-dihydrophenanthrene (17), 2, 7-dihydroxy-3, 4, 6-trimethoxy-9, 10-dihydrophenanthrene (18), 4, 5-dihydroxy-2, 3-dihydroindenespiro-3'-methoxy-4', 5'-methylenedioxy-3', 5'-diene-cyclohex-2'-one (19)*, (+)-lyoniresinol-3a-O-B-D-glucopyranoside (20), 3-hydroxyphenethyl alcohol 3-O-(6'-O-p-D-apioruranosyl)-p-D-glucopyranoside (21)*, 3-methoxyphenethyl alcohol 4-O-B-D-glucopyranoside (22), 3, 5-dimethoxyphenethyl alcohol 4-0-p-D-glucopyranoside (23), syringin (24), p-hydroxy-phenylpropionic acid (25), p-hydroxyphenylpropionic methyl ester (26), 3-methoxy-4-hydroxycinnamic aldehyde (27), 4-hydroxy-2, 6-dimethoxybenzaldehyde (28), orsellinic ethyl ester (29), respectively. 1,2,12,19 and 21 are new compounds, 8, 9,14,17,18, 20, 22-29 were isolated from Bulbophyllum genus for the first time.
    Among the 53 compounds, triterpenoid saponins from A. crenata Sims showed potent activity against Pyricularia oryzae, however, bibenzyls, phenanthrenes and dihydrophenanthrenes from Bulbophyllum odoratissimum Lindl. had relatively very weak activity.
    MTT method was also used to test the cytotoxic activity of these compounds on MCF-7, NCI-H460 and SF-268 cancer cell lines recommended by NCI. Triterpenoid saponins from A. crenata Sims also showed strong cytotoxic activities. Bibenzyl, phenanthrene and dihydrophenanthrene from B. odoratissimum Lindl. were inactive except that 3'-hydroxy-3-methoxy-4, 5-methylenedioxybibenzyl (5) and 5'-hydroxy-5-methoxy-2, 2'-oxrpin-3, 4- methylenedioxybibenzyl(7) had relatively weak activity. The cytotoxicity on HepG2 and Hep3B cell lines, two kinds of human li
引文
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