多穗金粟兰的化学成分研究
详细信息    本馆镜像全文|  推荐本文 |  |   获取CNKI官网全文
摘要
本论文第一章综述了金粟兰科金粟兰属植物的化学成分和生物活性研究进展,对1979-2009年期间从该属植物中分离鉴定的170余个化合物进行了归纳整理,并根据结构特点进行了分类。
     本论文第二章对金粟兰科(Chloranthaceae)金粟兰属(Chloranthus)植物多穗金粟兰(Chloranthus multistachys)的化学成分进行了系统深入的研究。利用各种色谱分离技术,从多穗金粟兰全株的甲醇提取物中分离得到37个单体化合物,并通过现代波谱技术(1D-NMR,2D-NMR, MS, UV, IR等)鉴定了其结构,包括16个新化合物。化合物结构类型涉及倍半萜、倍半萜二聚体、苯丙素、木脂素、黄酮、酚性化合物、甾体等。这37个化合物的结构分别为:多穗金粟兰醇B-G (chloramultiols B-G,1-6), chloramultilide C (7), chloramultilide D (8),银线草醇B (shizukaol B,9),环银线草醇A(cycloshizukaol A,10),多穗金粟兰内酯A-I (multistalactone A-Ⅰ,11-19),长尾粗叶木内酯A (lasianthuslactone A,20),1β,4β-二羟基-5α-氢-7(11)-桉叶烯-8α,12-内酯(1β,4β-dihydroxy-5α(H)-eudesm-7(11)-en-8α,12-olide,21),1β,4α-二羟基-5α-氢-7(11)-桉叶烯-8α,12-内酯(1β,4α-dihydroxy-5α(H)-eudesm-7(11)-en-8α,12-olide,22),1β,10α:4α,5β-二坏氧-6β-羟基吉玛烷-8,12-内酯(1β,10α:4α,5β-diepoxy-6β- hydroxyglechoman-8a,12-olide,23),20,22-异丙叉基筋骨草甾酮C (ajugasterone C-20,22-acetonide,24),β-蜕皮甾酮(β-ecdysterone,25),2,3:20,22-双异丙叉基-24-表-蝶甾酮(24-epi-pterosterone-2,3,20,22-diacetonide,26),2,3:20,22-双异丙叉基-β-蜕皮甾酮(20-hydroxyecdysterone-2,3,20,22-diacetonide,27),丁香酸-4-O-α-L-鼠李吡喃糖苷(syringic acid-4-O-α-L-rhamnopyranoside,28),迷迭香酸(rosmarinic acid,29),迷迭香酸甲酯(methyl rosmarinate,30),枸橼苦素(citrusin C,31),苯乙醇-8-氧-β-D-葡萄糖苷(phenethyl-8-O-β-D-glucopyranoside,32),3,4-二氧-异丙叉基莽草酸(3,4-O-isopropylidenyl shikimic acid,33),松脂素(penoresinol,34),丁香脂素(dihydrodehydrodiconifery alcohol,35),2'-羟基-4,4′,6′-三甲氧基查耳酮(2'-hydroxy-4,4',6'-trimethoxy-chalcone,36),甘油(glycerol,37)。其中多穗金粟兰醇G(6)是一个结构新颖的8,9-断裂的乌药烷型倍半萜二聚体,并推导了其可能的生物合成途径。
This dissertation consists of two chapters. Chapter 1, reviewed the progress on the phytochemistry study and pharmacological activities from the genus Chloranthus.
     Chapter 2, phytochemical investigation on Chloranthus multistachys (Chloranthaceae) have lead to 37 compounds, including 6 new lindenane-type sesquiterpenoid dimmers,9 new sesquiterpenoids, and a new phenolic glycoside. Among them, chloramutiol G (6) was a novel 8,9-seco-lindenane-type sesquiterpenoid dimmer. These compounds were identified as follows:chloramultiol B-G (1-6), chloramultilide C (7), chloramultilide D (8), shizukaol B (9), cycloshizukaol A (10), multistalactone A-Ⅰ(11-19), lasianthuslactone A (20), 1β,4β-dihydroxy-5a(H)-eudesm-7(11)-en-8a,12-olide (21),1β,4a-dihydroxy-5a(H)-eudesm-7(11)-en-8a,12-olide (22), 1β,10a:4a,5β-diepoxy-6β-hydroxyglechoman-8a,12-olide (23), ajugasterone C-20,22-acetonide (24),β-ecdysterone (25),24-epi-pterosterone-2,3:20,22-diacetonide (26),20-hydroxyecdysterone-2,3:20,22-diacetonide (27), syringic acid-4-O-a-L-rhamnopyranoside (28), rosmarinic acid (29), methyl rosmarinate (30), citrusin C (31), phenethyl-8-O-β-D-glucopyranoside (32),3,4-O-isopropylidenyl shikimic acid (33), (-)-Penoresinol (34), (-)-(7S,8R)-dihydrodehydrodiconifery alcohol (35),2'-hydroxy-4,4', 6'-trimethoxychalcone (36), and glycerol (37).
引文
[1]中国科学院中国植物志编辑委员会.中国植物志[M].北京:科学出版社,1982,20,p79-80.
    [2]《全国中草药汇编》编写组.全国中草药汇编[M].北京:人民卫生出版社,1975.p549
    [3]Kawabata J, Tahara T. Lactones with lindenene structure. Compositions of Chloranthus japonicus [J]. Kagaku to Seibutsu,1979,17(11):699-700.
    [4]Kawabata J, Tahara S, Mizutani J. Isolation and structural elucidation of four sesquiterpenes from Chloranthus japonicus (Chloranthaceae)[J]. Agricultural Biology and Chemistry,1981,45(6):1447-1453.
    [5]Yang S, Gao Z, Wang F, et al. Chlorahololides A and B, Two Potent and Selective Blockers of the Potassium Channel Isolated from Chloranthus holostegius[J]. Organic Letters,2007,9(5):903-906.
    [6]Kwon O. E, Lee H. S, Lee S. W, et al. Dimeric sesquiterpenoids isolated from Chloranthus japonicus inhibited the expression of cell adhesion molecules[J]. Journal of Ethnopharmacology,2006,104(1):270-277.
    [7]Wu B, Chen J, Qu H. B, et al. Complex Sesquiterpenoids with Tyrosinase Inhibitory Activity from the Leaves of Chloranthus Tianmushanensis[J]. Journal of Natural Products,2008,71(5):877-880.
    [8]Yang S, Yue J. Chloramultilide A, a highly complex sesquiterpenoid dimmer from Chloranthus multistachys[J]. Tetrahedron Letters,2006,47(7):1129-1132.
    [9]Yang S. P, Yue J. M. Terpenoids from Chloranthus mutistachys[J]. Natural Product Research,2008,22(13):1163-1168.
    [10]罗永明,.李创军,黄璐琦.金粟兰科药用植物的研究概况[J].江西中医学院学报,2007,19(1):64-67.
    [11]Masaaki U, Yutaka K, Genjiro K, et al. Studies on the Constituents of Chloranthus spp.Ⅲ Six sesquiterpenes from Chloranthus japonicus [J]. Chemical& Pharmaceutical Bulletin,1980,28(1):92-102.
    [12]Kawabata J, Fukushi Y, Tahara S. et al. Shizukaol a, a sesquiterpene dimer from Chloranthus japonicus[J]. Phytochemistry,1990,29(7):2332-2334.
    [13]Kawabata J, Fukushi Y, Mizutani J. Sesquiterpene dimer and trimer from Chloranthus japonicus[J]. Phytochemistry,1998,47(2),231-235.
    [14]Kawabata J, Mizutani J. Distribution of lindenanolides in the Chloranthaceae[J]. Agricultural Biology and Chemistry,1988,52, (11),2965-2966.
    [15]Kawabata J, Mizutani J. Studies on the chemical constituents of Chloroanthaceae plants. Part Ⅵ. Shizukanolides D, E and F, novel lindenanolides from Chloranthus spp. (Chloranthaceae) [J]. Agricultural Biology and Chemistry,1989,53(1): 203-207.
    [16]Takeda Y, Yamashita H, Matsumoto T, et al. Chloranthalactone F, a sesquiterpenoid from the leaves of Chloranthus glaber[J]. Phytochemistry,1993,33(3),713-715.
    [17]Kawabata J, Fukushi E, Mizutani J. Symmetric sesquiterpene dimer from Chloranthus serratus[J]. Phytochemistry,1993,32(5):1347-1349.
    [18]Uchida M, Koike Y, Kusano G, et al. Six sesquiterpenes from Chloranthus japonicus[J]. Chemical& Pharmaceutical Bulletin,1980,28(1):92-102.
    [19]Kawabata J, Tahara S, Mizutani J, et al. Shizukanolides, two sesquiterpenoids from Chloranthus japonicus (Chloranthaceae) [J]. Agricultural Biology and Chemistry, 1979,43(4):885-887.
    [20]Tahara S, Fukushi Y, Kawabata J, et al. Lindenanolides in the root of chloranthus japonicus (Chloranthaceae)[J]. Agricultural Biology and Chemistry,1981,45(6): 1511-1512.
    [21]Wang X. C, Wang L. L, Ouyang W. X,.et al. Sesquiterpenes and Dimers Thereof from Chloranthus fortunei[J]. Helvetica Chimica Acta,2009,92(2):313-319.
    [22]Kuang H. X, Xia Y. G, Yang B. Y, et al. Sesquiterpene Glucosides from Chloranthus japonicus Sieb[J]. Chemistry& Biodiversity,2008,5(9):1736-1742.
    [23]Okamura H, Nakashima N, Iwagawa T, et al. The structures of two lindenane sesquiterpene glucosides from Chloranthus glaber[J]. Chemistry Letters,1994,23(8): 1541-1542.
    [24]Kawabata J, Fukushi Y, Tahara S, et al. Structures of novel sesquiterpene ketones from Chloranthus serratus (Chloranthaceae)[J]. Agricultural Biology and Chemistry,1985, 49(5):1479-1485.
    [25]Kusano G, Abe M, Koike Y, et al. Studies on the constituents of Chloranthus spp. Further studies on the constituents of Chloranthus japonicus[J]. Yakugaku Zasshi 1991,111(12),756-764.
    [26]Wu B, He S, Wu X, et al. Cadinane and eudesmane sesquiterpenoids from Chloranthus henryi[J]. Helvetica Chimica Acta,2007,90(8),1586-1592.
    [27]Kawabata J, Fukushi Y, Tahara S, et al. Structures of novel sesquiterpene alcohols from Chloranthus japonicus[J]. Agric Biol Chem,1984,48(3):713-717.
    [28]李创军,张东明,罗永明,宽叶金粟兰化学成分的研究[J].药学学报,2005,40(6),525-528.
    [29]Wu B, He S, Pan Y. Sesquiterpenoid with new skeleton from Chloranthus henryi[J]. Tetrahedron Letters,2006,48(3),453-456.
    [30]Wu, B.; He, S.; Wu, X.; Pan, Y, Bioactive terpenes from the roots of Chloranthus henryi[J]. Planta Medica.2006,72(14),1334-1338.
    [31]Tesso H, Koenig W. A, Son P. T, et al. Composition of the essential oil of flowers of Chloranthus spicatus (Thunb.) Makino[J]. Flavour and Fragrance Journal,2006, 21(4),592-597.
    [32]Wu B, He S, Wu X. D, Pan Y. J. New Tyrosinase Inhibitory Sesquiterpenes from Chloranthus henryi[J]. Chemistry& Biodiversity,2008,5(7):1298-1303.
    [33]Yang S. P, Zhang C. R, Chen H. D, et al. Sesquiterpenoids from Chloranthus spicatus (Thunb.) Makino[J]. Chinese Journal of Chemistry,2007,25(12):1892-1895.
    [34]Yuan T, Zhang C. R, Yang S. P, et al. Sesquiterpenoids and Phenylpropanoids from Chloranthus serratus[J]. Journal of Natural Products,2008,71(12):2021-2025.
    [35]Wu B, Qu H. B, Cheng Y. Y. New Sesquiterpenes from Chloranthus japonicus[J]. Helvetica Chimica Acta,2008,91(4):725-732.
    [36]Takemoto T, Uchida M, Kusano G. Studies on the constituents of Chloranthus spp. II. The sesquiterpenes from Chloranthus serratus[J]. Chemical& Pharmaceutical Bulletin,1976,24(3):531-533.
    [37]Wu B, He S, Wu X, et al. Cadinane and eudesmane sesquiterpenoids from Chloranthus henryi[J]. Helvetica Chimica Acta,2007,90(8):1586-1592.
    [38]Wu B, He S, Pan Y. J. Sesquiterpenoid with new skeleton from Chloranthus henryi[J], Tetrahedron Letters,2007,48(26):453-456.
    [39]Kawabata J, Fukushi Y, Tahara S, et al. Studies on the chemical constituents of Chloranthaceae. Part 7. Shizukaol A, a sesquiterpene dimer from Chloranthus japonicus[J]. Phytochemistry,1990,29(7):2332-2334.
    [40]Kawabata J, Fukushi E, Mizutani J. Sesquiterpene dimers from Chloranthus japonicus[J]. Phytochemistry,1995,39(1):121-125.
    [41]Kawabata J, Mizutani J. Dimeric sesquiterpenoid esters from Chloranthus serratus[J]. Phytochemistry,1992,31(4):1293-1296.
    [42]Okamura H, Iwagawa T, Nakatani M. A revised structure of chloranthalactone F and chloranthalactone A photodimer[J]. Bulletin of The Chemical Society of Japan,1995, 68(12):3465-3467.
    [43]Wang X. C, Zhang Y. N, Wang L. L, et al. Lindenane Sesquiterpene Dimers from Chloranthus fortunei[J]. Journal of Natural Products,2008,71(4):674-677.
    [44]Xu Y. J, Tang C. P, Ke C. Q, et al. Mono-and Di-sesquiterpenoids from Chloranthus spicatus[J]. Journal of Natural Products,2007,70(12):1987-1990.
    [45]Yang S. P, Gao Z. B, Wang F. D, et al. Chlorahololides A and B, Two Potent and Selective Blockers of the Potassium Channel Isolated from Chloranthus Holostegius[J]. Organic Letters,2007,9(5):903-906.
    [46]Yang S. P, Gao Z. B, Wu Y, et al. Chlorahololides C-F:a new class of potent and selective potassium channel blockers from Chloranthus holostegius[J]. Tetrahedron, 2008,64(9):2027-2034.
    [47]Li C. J, Zhang D. M, Luo Y. M, et al. Bis-sesquiterpenes and diterpenes from Chloranthus henryi[J]. Phytochemistry,2008,69(16):2867-2874.
    [48]Wu B, Chen-J, Qu H. B, et al. Complex Sesquiterpenoids with Tyrosinase Inhibitory Activity from the Leaves of Chloranthus Tianmushanensis[J]. Journal of Natural Products,2008,71(5):877-880.
    [49]Kim S. Y, Kashiwada Y, Kawazoe K, et al. Spicachlorantins A and B, new dimeric sesquiterpenes from the roots of Chloranthus spicatus[J]. Phytochemistry letters, 2009,2(3):110-113.
    [50]Wang X. C, Wang L. L, Ouyang X. W, et al. Sesquiterpenes and Dimers Thereof from Chloranthus fortunei[J]. Helvetica Chimica Acta,2009,92(2):313-319.
    [51]Takemoto T, Uchida M, Koike K, et al. Constituents of Chloranthus species. Ⅰ. Structures of two new amides from Chloranthus serratus and the isolation of isofraxidin from C. japonicus[J]. Chemical& Pharmaceutical Bulletin,1975,23(5), 1161-1163.
    [52]Gao C. W, Chen Y. S, Xie J. M, et al. Studies on the Chemical Constituents of the Chloranthus Holostegius[J]. Chemical Journal of Chinese Universities,1987,8(2): 141-142.
    [53]Sashida Y, Shimomura H, Nukaga K, et al. The constituents of Chloranthus glaber and its preparation[J]. Shoyakugaku Zasshi,1981,35 (3):217-220.
    [54]姚淦,王铁增.我国华东地区金粟兰科药用植物的鉴定[J].中草药,1983,14(8):35中草药,1983,14(8):35-37.
    [55]李松林,崔熙,乔传卓,等.五种金粟兰属植物挥发油成分及其抗真菌活性研究[J].中药材,1992,15(7):28-30.
    [56]Tahara, Fukushi Y, Kawabata J, et al. Lindenanolides in the root of Chloranthus japonicus[J]. Agricultural Biology and Chemistry,1981,45(6):1511-1514.
    [57]刘启,韩定献,苏明武,等.宽叶金粟兰收缩子宫成分的研究[J].中国医院药学报杂志,1994,14(11):509.
    [58]Kawabata J, Tahara T. Lactones with lindenene structure. Compositions of Chloranthus japonicus. Kagaku to Seibutsu,1979,17(11),699-700.
    [59]乐兆升,刘娴芳.53种中草药抗血小板聚集作用的初步观察[J].中药通报,1985,10(1):44-45.
    [60]中国科学院中国植物志编委会,中国植物志[M],北京:科学出版社,1982,20(1):p91-93.
    [61]Xu Y. J, Tang C. P, Ke C. Q, et al. Mono-and Di-sesquiterpenoids from Chloranthus spicatus[J]. Journal of Natural Products,2007,70 (12):1987-1990.
    [62]李斌,张东明,罗永明.长尾粗叶木根一个新倍半萜内酯的分离[J].药学学报,2006,41(5):426-430.
    [63]Ei-Gamal A. A. Sesquiterpene lactones from Smyrnium olusatrum[J]. Phytochemistry, 2001,57(8):1197-1200.
    [64]谭成玉,王金辉,李铣,等.露水草的化学成分[J].药学学报,2003,38(10):760-762.
    [65]黄孝春,郭跃伟,周文亮,等.苍白秤钩风脱皮甾酮类化学成分的研究[J].天然产物研究与开发,2003,15(2):93-97.
    [66]Suksamrarn A, Yingyongnarongkul B, Charoensuk S. Regioselective systhesis of 24-epi-Pterosterone[J]. Tetrahedron,1999,55(1):255-260.
    [67]Tomas J, Camps F, Coll J, et al. Synthesis of 25-fluroponasterone A, a fluorinated analogue of 20-hydroxyecdysone[J]. Tetrahedron,1992,48 (44):9809-9818.
    [68]黄明菊,李妍岚,曾光尧,等.肿节风化学成分研究[J].中南药学,2007,5(5):459-461.
    [69]李丽,许利嘉,贺震旦,等.紫草科苦丁茶-厚壳树醋酸乙酯部位化学成分研究[J].中国中药杂志,2008,33(17):2121-2123.
    [70]尹永芹,罗建光,孔令义.甘薯的化学成分研究[J].中草药,2007,38(4):508-510.
    [71]李艳,赵庆春,郭涛,等.大青根化学成分的研究[J].中国药物化学杂志,2008,18(5):371-373.
    [72]王静,彭树林,王明奎,等.金丝桃的化学成分[J].中国中药杂志,2002,27(2):120-122.
    [73]朱丽萍,李媛,杨敬芝,等.草珊瑚的化学成分研究[J].中国中药杂志,2008,33(2):155-157.
    [74]Hu X J, Jin H Z, Zhang W, et al. Chemical constituents from Daphne korena Nakai[J]. Chinese Journal of Natural Medicines,2008,6(6):411-414.
    [75]李晓明,刘健美,张翼,等.米仔兰化学成分研究[J].中草药,2007,38(3):356-357.
    [76]Su Z. S, Yin S, Zhou Z. W, et al. Sesquiterpenoids from Hedyosmum orientale. [J]. Journal of Natural Products,2008,71(8):1410-1413.
    [77]邵莉,黄卫华,张朝凤,等.兜唇石斛的化学成分研究[J].中国中药杂志,2008,33(14):1693-1695.
    [78]Kasai R, Okihara M, Asakawa J, et al.13C NMR study of α-andβ-anomeric pairs of D-mannopyranosides and L-rhamnopyranosides[J]. Tetrahedron,1979,35 (11): 1427-1432.
NGLC 2004-2010.National Geological Library of China All Rights Reserved.
Add:29 Xueyuan Rd,Haidian District,Beijing,PRC. Mail Add: 8324 mailbox 100083
For exchange or info please contact us via email.