A new guaiane diterpenoid from Euphorbia wallichi

A new guaiane-type diterpenoid, (1 alpha, 5 alpha, 7 alpha)-3,10(18), 11-dictytriene-19-acid, was obtained from the roots of Euphorbia wallichii. This is the first isolation of guaiane diterpene from this genus of Euphorbia. The structure was elucidated by spectral methods. And the compound was tested for the cytotoxicities on the cancer cell line P-388 and A-549 in vitro.

Tetranorclerodanes and clerodane-type diterpene glycosides from Dicranopteris dichotoma

The acetone extract of Dicranopteris dichotoma afforded two new tetranorclerodanes, 18-hydroxyaylthonic acid (1) and 18-oxo-aylthonic acid (2), and four new clerodane-type diterpene glycosides, (6S,13S)-6-O-[6-O-acetyl-beta-D-glucopyranosyl-(1 -> 4)-alpha

A novel hydroperoxyl substituted cembranolide diterpene from marine soft coral Lobophytum crassum

A new cembranolide diterpene with a hydroperoxyl substitution was isolated from the marine soft coral Lobophytum crassum. The structure was elucidated on the basis of chemical and spectral methods.

An ent-Kaurane Diterpene from Euphorbia wallichii

One known ent- kaurane diterpene, ent- 16α, 17- dihydroxykauran- 3-one, were isolated from the roots of Euphorbia wallichii for the first time. Its structure was elucidated on the basis of spectral methods. And the NMR assignments of the compound in CD3OD were given for the first time.

A new daphnane diterpene from Daphne tangutica

A new daphnane diterpene was isolated from the root barks of Daphne tangutica Maxim. Its structure was elucidated as 1, 2 alpha-dihydro-20-palimoyldaphnetoxin by the spectroscopic evidence including 2D-NMR.

附子及乌头属植物中二萜类生物碱的电喷雾质谱研究

电喷雾质谱是一种软电离技术，生物碱分子中均含有氮原子，具有很高的质子亲合势和气相碱度，特别适合电喷雾质谱分析。本文利用电喷雾质谱系统研究了乌头属的几种植物中二菇类生物碱的质谱行为。并且对中药复方中的生物碱成分的化学变化进行探讨，在串联质谱中，乌头碱类生物碱的裂解方式相似。双酷型、三醋型、脂类生物碱在MS2中容易丢失C8乙酸或长链脂肪酸形成特征子离子峰，在进一步CID谱中，在C15位失去CO为其特征。但是单酷型生物碱在串联质谱中碎裂方式与上述几种生物碱有很大差别，例如，在MSZ中主要失去甲醇，还会失去C3位经基，但是不会失去CS轻基。利用这些规律分析了附子及草乌中的生物碱，发现了多种具有特殊取代基的新化合物。以电喷雾质谱为检测手段分析了附子在炮制过程中的成分变化；并且发现了分离提取脂类生物碱的方法。高乌头中的生物碱以C18型为主，同时也包含少量C19乌头碱骨架的生物碱。这两种类型的生物碱在串联质谱中的碎裂规律相似，都容易失去取代基，而生物碱骨架比较稳定，难以碎裂。但是不同位置的取代基失去时所形成的子离子的丰度有很大差别，经过串联质谱可以获取重要的结构信息。并且通过串联质谱确定了刺乌头碱环糊精的包合位点，更正了文献中的错误。关白附的CZ。型海替生型生物碱在串联质谱中的行为与上述生物碱相似，容易失去取代基，但是在失去取代基的同时，常常伴随骨架中C-C键的断裂。由于这些生物碱的结构存在较强的规律，所以很容易表征其中的结构相似的新生物碱。另一方面，我们发现导致白术与附子配伍将导致共煎液中有毒生物碱成分增加，从而解释了八味地黄丸与人参汤导致中毒的原因。并且通过对八味地黄汤的配伍研究，发现起解毒作用的药材为山茱英，解毒机理为抑制了有毒生物碱的溶出。方中的山药能够抑制双酷型生物碱的水解。

水菖蒲的化学成分研究和忍冬属植物的色谱分析

本论文由三章组成。第一章阐述了藏药水菖蒲的化学成分研究，共分离鉴定了39个化学成分，其中6个为新化合物。第二章报道了几种忍冬属植物的HPLC、HPLC-MS、GC分析以及抑菌活性、重金属含量测定结果。第三章概述了菖蒲属植物的研究进展。 第一章报道了水菖蒲(Acorus calamus L.)化学成分的分离纯化与结构鉴定。采用正、反相硅胶柱层析等分离方法，从水菖蒲的根中共分离出41个化合物，通过红外、质谱、核磁共振及X-ray单晶衍射等波谱方法和模拟计算方法鉴定了其中39个化合物的结构，主要为倍半萜、苯丙素、甾体类化合物。其中含有5个新的倍半萜类化合物和1系列新的甾体皂苷衍生物。经波谱分析将它们的结构鉴定为 1b, 7a(H)-cadinane-4a, 6a, 10a-triol (1), (2R,6R,7S,9S)-1(10), 4-cadinadiene-2, 9-diol (2), 1a, 5b-guaiane-10a-O-ethyl-4b, 6b-diol (7), 6b, 7b(H)-cadinane-1a, 4a, 10a-triol (13)，(1R,4R,6S,10R)-1-hydroxy-7(11)-cadinen-5, 8-dione (14)， 4′-O-正n碳酰基-3-O- β-D-葡萄糖基谷甾醇(n=14, 16, 18, 22) (15)。 第二章包括四个部分。第一部分报道了忍冬属三种植物40个样品的HPLC测定和对主要活性成分绿原酸的定量分析结果，以及运用HPLC-MS技术对色谱图中8个峰进行指认。在此基础上，考察了种植和采收多个因素对绿原酸含量的影响。第二部分报道了忍冬属三种植物27个样品的GC分析，根据样品的挥发性成分的保留时间对不同样品进行了定性比较，并考察了花期及海拔高度对植物挥发性成分的影响。第三、四部分分别阐述了灰毡毛忍冬和红腺忍冬的体外抑菌活性研究和重金属含量测定结果。 第三章全面系统地概述了菖蒲属植物的化学成分和药理活性研究进展。 This dissertation is composed by three chapters. The first chapter elaborates the phytochemical investigation of Acorus calamus L. Thirty-nine compounds including six new compounds were isolated and identified. The second chapter reports the research on genus Lonicera by HPLC, HPLC-MS and GC. Antifungal activity and heavy metals measurement of genus Lonicera were reported. The third chapter is a review about the research progress on the plant family of Acorus. The first chapter focuses on the isolation and identification of chemical constituents from Acorus calamus L.. Forty-one compounds were isolated from the root of Acorus calamus L. by repeat column chromatography over normal and reversed phase silica gel, the structure of thirty-nine compounds was identified by spectroscopic methods and computational methods, including IR, MS, NMR and X-ray. Those compounds mainly belonged to sesquiterpene, phenylpropanoid and steroid. Among them, five are new sesquiterpenes and one series are new steroid glycoside derivatives. Their structure were suggested as 1b, 7a(H)-cadinane-4a, 6a, 10a-triol (1), (2R,6R,7S,9S)-1(10), 4-cadinadiene-2, 9-diol (2), 1a, 5b-guaiane-10a-O-ethyl-4b, 6b- diol (7), 6b, 7b(H)-cadinane-1a, 4a, 10a-triol (13), (1R,4R,6S,10R)-1-hydroxy-7(11)- cadinen-5, 8-dione (14), 4′-O-carbonyl-3-O-β-D-glucosyl-sitosterol (carbonyl = tetradecanoyl, hexadecanoyl, octadecyl, docosanoyl) (15). The second chapter consists of four parts. The first part reports the HPLC analysis of forty samples of the genus Lonicera, and the quantitative investigation of chlorogenic acid in these samples by HPLC analysis. Relationship between the content of chlorogenic acid in different samples and their planting conditions and harvesting time were discussed. Furthermore, eight compounds were identified or tentatively characterized based on their mass spectra and UV spectra profiles. The second part is about qualitative analysis of the volatile constituent in twenty-seven samples of genus Lonicera by GC. The effect of planting altitude and harvesting time on the volatile constituent was also investigated. The third and fourth parts describe the antifungal activity and content of some kinds of heavy metals of L. macranthoides Hand.-Mazz. and L. hypoglauca Miq.. The third chaspter is a review about the research progress of the plant family of Acorus.

唐古特瑞香和大果大戟的化学成分研究

本学位论文由两部分共3章组成。第一部分分别报道2种藏药唐古特瑞香和大果大戟化学成分的研究成果，从2种药用植物共分离鉴定了60个不同的化合物，其中12个为新结构，特别有意义的是发现了2个具有同一新骨架的二萜化合物。第二部分概述了大戟科植物多环二萜的研究进展。 第一部分包括第1和2章。在这2章中分别报道了唐古特瑞香（Daphne tangutica Maxim）和大果大戟（Euphorbia wallichii Hook. f. Fl）化学成分的分离纯化与结构鉴定。实验采用正、反相硅胶柱层析、薄层制备及HPLC等分离方法，从唐古特瑞香的根皮中共分离出32个化合物，通过红外、质谱及核磁共振等波谱方法鉴定了其中的31个，结构类型分别属于瑞香二萜类、木脂素类、香豆素类、苯丙素类及甾体类，其中有三个新的瑞香二萜型化合物，经波谱分析将它们的结构分别鉴定为1,2a-二氢-20-棕榈酰瑞香毒素、1,2a-二氢-5b-羟基-6a,7a-环氧-树脂大戟醇-14-苯甲酸酯及1,2b-二氢-5b-羟基-6a,7a-环氧-树脂大戟醇-14-苯甲酸酯，另外还有13个已知化合物为首次从该植物中分离得到。从大果大戟的根部共分离出33个化合物，鉴定了其中的30个，其主要成分为种类丰富的二萜，包括巨大戟烷型、续随子烷型、对映－阿替生烷型、对映－贝壳杉烷型、对映－松香烷型、ent-trachylobane型、对映－异海松烷型及一新骨架五环二萜ent-wallichane型，另外还有香豆素、甾体、三萜和一些简单的小分子化合物。其中新化合物有9个，经波谱分析将它们的结构分别鉴定为5-O-(2E,4E,6E)-癸三烯酰基-3,20-O-二乙酰基巨大戟醇、5-O-(2E,4Z)-癸二烯酰基-3-O-乙酰基-20-去氧巨大戟醇、3-O-(2E,4Z)-癸二烯酰基-5b,6b-氧-交京大戟醇、7-苯甲酰氧基-3,5,15-三乙酰基-续随子醇、ent-trachylobane-3-one-17-oic-acid、3α-羟基-对映-阿替斯-16-烯-14-酮、3α,6-二羟基-对映-异海松-7-烯-2,15-二酮、wallichanol A 和 wallichanol B，其中，wallichanol A 和 wallichanol B属于一新骨架类型的五环二萜。除此以外，另有13个已知化合物为首次从该植物中分离得到。 第2部分即第3章，首次概述了大戟属植物中多环二萜的化学和药理研究进展。 This dissertation is composed by two parts. The first part reports the phytochemical investigation of two Tibetan medicine plants, Daphne tangutica Maxim and Euphorbia wallichii Hook. f. Fl. Sixty different compounds including ten new compounds and two novel diterpenoids possessing a new carbon skeleton were isolated and identified. The second part is a review about the progress of studies on the polycyclic diterpeniods of the plant family of Euphorbia. The first part consists two chapters, which expatiate on the isolation and identification of chemical constituents from D. tangutica and E. wallichii. Thirty-one compounds were isolated from the root barks of D. tangutica by methods of column chromatography (silica gel, including reversed phase), preparative TLC and HPLC, and their structure were identified as nine daphnane diterpenes, six lignans, nine cumarin derivatives, five phenylpropanoid derivatives, a steroids and a benzoate on the basis of spectroscopic methods including IR, MS and NMR. Among them, three are new diterpenes with skeleton of daphnane and the structure were determined as 1,a-dihydro-20-palimoyl-daphnetoxin, 1,2a-dihydro-5b- hydroxy-6a,7a-epoxy-resiniferonol-14-benzoate and 1,2b-dihydro-5b-hydroxy- 6a,7a-epoxy-resiniferonol-14-benzoate. In addition, thirteen known ones were isolated from this plant for the first time. Isolation of the roots of E. wallichii yielded thirty compounds, twenty-four of them were elucidated as diterpenoids, which belong to different skeleton types of ingenol, lathyrane, ent-atisane, ent-kaurane, ent-abietane, ent-trachylobane, ent-isopimarane and a new pentacyclic skeleton ent-wallichane respectively. The remains including a cumarine, a triterpenoid, a steroid and three compounds with small molecule. Nine new compounds were characterized as 5-O-deca-2E,4E,6E- trienoyl-3,20-O-diacetylingenol, 5-O-deca-2E,4Z-dienoyl-3-O-acetyl-20- deoxyingenol, 3-O-deca-2E,4Z-dienoyl-jolkinol-5b,6b-oxide, 7-benzoyl-3,5,15- triacetyl-7-hydroxylathyrol, ent-trachylobane-3-one-17-oic-acid, 3α-hydroxy-ent- atis-16-en-14-one, 3α,6-dihydroxy-ent-isopimarane-7-en-2,15-dione, wallichanol A and wallichanol B, respectively, by means of comprehensive spectroscopic analysis. Among them, wallichanol A and wallichanol B were two notable novel pentacyclic diterpenoids processing a new rearranged carbon skeleton. And more, thirteen ones were firstly reported from this plant. The third chapter summarizes the research development on chemistry and pharmacology of polycyclic diterpenes from the plant family of Euphorbia for the first time.

天然产物Standishinal 的首次全合成研究

具有1，1，4α-三甲基氢化芴骨架结构的天然三环二萜化合物自然界中不常见。在该类化合物中，Standishinal 具有良好的芳香化酶抑制活性和细胞毒活性。迄今未发现有Standishinal 的全合成报道，因此，我们对Standishinal 的全合成进行了探索，在该过程中得到以下实验结果： 1. 发现MSA/P2O5、MSA 在无溶剂条件下，25 °C 时烷氧基苯即可实现向苯酚的转化，但在CH3NO2 中，温度升高至80 °C 并未发生反应。 2. 烷氧基苯或对溴苯酚与α-环香叶酸在不同温度下以MSA/P2O5、MSA、PPA为催化剂以CH3NO2 为溶剂或以BF3·Et2O为催化剂时均不发生Friedel-Crafts酰化反应。 3. 对溴苯酚与香叶酸在p-TsOH 催化作用下发生了香叶酸向α-环香叶酸环化、α-环香叶酸环与对溴苯酚的酯化，得到了唯一产物α-环香叶酸对溴苯酯，产率68%。 Standishinal is one of tricyclic-diterpenes possessing the uncommon 1, 1,4a-trimethylhydrofluorene skeleton. Standishinal possesses cytotoxic and aromataseinhibitory activities. Till now, no synthesis of standishinal has been reported. Inattempt to synthesize standishinal, the following phenomenon were observed: 1. Alkyloxybenzenes could be transformed into corresponding phenol at 25 °C inthe presence of MSA/P2O5 or MSA under solvent free condition. ButAlkyloxybenzenes are stable in presence of MSA/P2O5 or MSA in CH3NO2 even at 80 °C. 2. Friedel-Crafts acylation of alkyloxybenzenes and p-bromophenol withα-cyclogeranic acid could not be realized under catalysis of MSA/P2O5, MSA or PPAin CH3NO2, or under catalysis of BF3·Et2O without CH3NO2. 3. The reaction of 4-bromaophenol and geranic acid in the presecnce of p-TsOHafforded 4-bromophenol α-cyclogeranoate in which cyclization of geranic acid toα-cyclogeranic acid was followed by esterification of α-cyclogeranic acid with p-bromophenol.