密 级： 学校代码：10075 分类号： 学 号：20091035 理学硕士学位论文 黄顶菊化感物质研究 学位申请人：吴亚丽 指 导 教 师 ：罗都强 教授 学 位 类 别 ：理学硕士 学 科 专 业 ：植物学 授 予 单 位 ：河北大学 答 辩 日 期 ：二一二年六月 Classified Index: CODE: 10075 U.D.C.: NO: 20091035 A Dissertation for the Degree of M.Science Study on Allelochemicals of Flaveria bidentis Candidate: Wu Yali Supervisor: Prof. Luo Duqiang Academic Degree Applied for : Master of Science Specialty: Botany University: Hebei University Date of Oral Examination:June, 2012 摘 要 I 摘 要 黄顶菊 Flaveria bidentis (L.) Kuntze 属菊科堆心菊族黄顶菊属，该属共有 21 种,主 要分布于北美南部等热带地区（Powell，1978），1 种在我国归化，即黄顶菊。2005 年 -2007 年在河北省大面积扩散，成为一种外来入侵植物，通过释放化感物质影响本地土 著植物的生长，对我国的生态安全造成严重的威胁。作为一种入侵植物，国内对黄顶菊 的研究主要集中在危害与防除方面， 而对黄顶菊化学成分的研究鲜有报道，研究最多的 是类黄酮和噻吩类化合物，对黄顶菊化感作用的研究也仅限于各种水提液及粗提物，因 此在前人的研究基础上本论文对其化学成分进行了分离提取鉴定， 并对黄顶菊化感物质 最新研究进展进行了综述，以期为进一步探索其防控和利用的途径提供参考，使其在得 到有效控制的情况下能够变废为宝，更多为人类生活提供服务。 本实验过程中采用常压硅胶柱层析，Sephadex LH-20 凝胶过滤，制备薄层层析， 半制备型 HPLC 等方法对黄顶菊的化感物质进行了研究，从该植物的乙醇提取物中共 分离了 20 个单体化合物，其中包括 1 个新化合物。这些化合物除化合物 12 （-terthienyl）以外，均为国内首次报道的黄顶菊的化学成分。这些化合物包括黄酮类 化合物 5 个，甾醇类化合物 5 个，噻吩类化合物 4 个，三萜类化合物 2 个，倍半萜类化 合物 1 个，含氮化合物 1 个，酚类化合物 1 个及酯类化合物 1 个，其中化合物 13 为新 化合物，是一种噻吩类物质。 通过经典的波谱手段，如 1H-NMR、13C-NMR、DEPT ，EI-MS，HMBC， HSQC，HMBC，1H-1H COSY，鉴定出这些化合物的结构，已知化合物分别为： -Caryophyllene 8R, 9R-Oxide(1)，a -Amyrin(2)，3-epi-betulinic acid(3)，Stigmastan-4-en- 3-one(4), 3-hydroxy-ergosta-5, 7, 22-triene(5)，3-hydroxy-5, 8-ergosta-6, 22-diene(6)， -sit- osterol(7)，(24S)-24methylcholest-7-ene-3ol(8)，1-methyl-2-pyrolidone(9)，1-(4- hydroxy-phenyl)ethanone(10)，4-Hydroxyphenethyl tetradecanoate(11)，-terthienyl(12)， 5, 6, 7-tri-hydroxy-2-(4-hydroxyphenyl)-4H-chromen-4-one(14) ， 7, 8-trihydroxy-2-(4- hydroxy-phenyl)-6-methoxy-4H-chromen-4-one(15) ， medicarpin(16) ， 5-(3-hydroxy-4- acetoxybutyne-1)-bithio- phene(17) ， 5-(3,4-diacetoxybut-1-ynyl)-2,2-bithiophene(18) ， 3-(4-hydroxyphenyl)-1-(2,4,6-trihydroxyphenyl)propan-1-one(19)，3, 5, 7-trihydroxy-2-(2- 摘 要 II hydroxy-4-methoxyphenyl-4)H-chromen-4-one(20)；新化合物命名为：2-methoxy-2-(5- (prop-1-yn-1-yl)-2,2-bithiophen-5-yl)ethanol(13)。 关键词 黄顶菊 化感物质 黄酮 噻吩 Abstract III Abstract Flaveria bidentis (L.) Kuntze is a genus of plants in the Asteraceae family, The genus Flaveria comprises 21 Species, native to the Southern North America and other tropical regions (Powell, 1978). One species owned by technology in China, bidentis. It Spreads a large area in Hebei Province in 2005-2007, becoming a kind of alien invasive plants, Through the release of allelochemicals, it affects the growth of the local indigenous plants, and the ecological security of our country face a serious threat. As an invasive plant, the domestic research of Flaveria bidentis focuses on the hazards and controlin, chemical constituents are rarely reported, the most studied compounds are flavonoids and thiophene. The allelopathy is limited to a variety of water extract and crude extracts. This thesis, on the basis of the previous studies, studies the separation, extraction and identification on their chemical compositionthe, and the latest research progress about allelochemicals of F. bidentis were reviewed in order to provide reference for the further exploration on the ways of its prevention, control and use. So that we can change chanwaste into treasure except effective control, and provide more services to human life. In the research, many chromatography methods are used for the isolation of Allelochemicals, including silica gel column method, Sephadex LH-2.0, preparation TCL, semi -preparation HPLC, then from the alcohol extract of, 20 compounds were isolated and elucidated, Including a new compound. They are all reported for the first time as the chemical compositiones of F. Bidentis. Including 5 flavonoids, 5 sterols, 4 thiophenes, 2 triterpenoids, 1 sesquiterpene compound, 1 nitrogenous compound, 1 phenolic compounds and1 ester compound, Among them, the new compound13 blong to thiophene. With the help of the spectral technolgy, including 1H-NMR、13C-NMR、DEPT ， El-MS，HMBC，HSQC，HMBC and COSY, the structure of these compounds are Identified, the known compounds are: -Caryophyllene 8R, 9R-Oxide (1), gosta-5,7,22-triene (5), 3-hydroxy-5, 8-ergosta-6, 22-diene (6), -sitosterol (7), (24S)- 24methylcholest -7- ene-3ol (8), 1-methyl-2-pyrolidone (9), 1-(4-hydroxyphenyl) -ethanone (10), 4- Hydroxyphenethyl tetra-decanoate (11), -terthienyl (12), 5, 6, 7-trihydroxy-2-(4- hydroxyphenyl)-4H-chromen-4-one (14), 7, 8-trihydroxy-2-(4-hydroxyphenyl)-6-methoxy- 4H-chromen-4-one (15), medicarpin (16), 5-(3-hydroxy-4-acetoxybutyne-1） -bithiophene (17), Abstract IV 5-(3, 4-diacetoxybut-1-ynyl)-2, 2-bithiophene(18) ， 3-(4-hydroxyphenyl)-1-(2, 4, 6- trihydroxyphenyl) propan-1-one (19) and 3, 5, 7-trihydroxy-2- (2- hydroxy-4- methoxyphenyl) -4H- chromen-4-one (20); the new