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.

Diterpenoids from Euphorbia wallichii

Object To study the chemical constituents of Euphorbia wallichii.Methods The constituents were repeatedly separated and purified on silica gel column.They were identified on the basis of spectral methods.Results Nine diterpenoids were obtained from the roots of E. wallichii.Among them jolkinol B(I) is lathyrane type;caudicifolin (Ⅱ),helioscopinolides A(Ⅲ),C(Ⅳ),and E(Ⅴ) belong to abietane type;while ent-atisane-3β,16α,17-triol(Ⅵ),ent-16α,17-dihydroxyatisan-3-one(Ⅶ),ent-3β,(13S)-dihydroxyatis-16-en-14-one(Ⅷ),and ent-2-hydroxy-atis-1,16(17)-dien-3,14-dione(Ⅸ) possess an ent-atisane skeleon.Conclusion All of them are isolated from E. wallichii for the first time.

Chemical constituents from euphorbia wallichii

Eleven known compounds were isolated from the roots of Euphorbia wallichii for the first time. They were elucidated to be three triterpenoids, β-amyrin (1), β-amyrin acetate (2) and 3β-acetoxy-lupenol (3), one nor-triterpene peroxide baccatin (4), two caffeic esters (5a, 5b), palmitic acid-2,3-dihydroxypropanenyl ester (6), palmitic acid (7), scopoletin (8), β-sitosterol (9) and daucosterol (10) on the basis of spectral methods. Among them, compound 5a, 5b were reported firstly in the spurge family. And the NMR assignments of compounds 5a and 5b were given for the first time.

Skeleton-rearranged pentacyclic diterpenoids possessing a cyclobutane ring from Euphorbia wallichii

Two novel rearranged trachylobane diterpenoids, designated as wallichanol A (2) and wallichanol B (3), consisting of an unprecedented pentacyclic skeleton named wallichane with a cyclobutane ring, and a new ent-trachylobane diterpenoid, 3-oxo-ent-trachyloban-17-oic acid (1), were isolated from the roots of Euphorbia wallichii. Their structures were elucidated by comprehensive analysis of 2D-NMR spectroscopic data, with the stereochemistry of 1 confirmed by X-ray crystallographic study. All of these compounds potently block osteoclastogenesis in vitro, suggesting a potential therapeutic application in prevention of osteoporosis.

Three new diterpenoids from Euphorbia wallichii

Three new abietane diterpene lactones, 3alpha-hydroxyjolkinolide A (1), ent-8alpha,14beta-dihydroxy-13(15)-ene-16(12alpha)-abietanolide (2) and ent-8alpha,14alpha-dihydroxy-13(15)-ene-16(12alpha)-abietanolide (3) as well as a known abietane diterpene jolkinolide A (4) were isolated from the roots of Euphorbia wallichii. Their structures were elucidated on the basis of spectroscopic analysis.

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.

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.

藏药大果大戟中的巨大戟烷型二萜酯类成分

目的研究藏药大果大戟Euphorbia wallichii丙酮提取物中的化学成分。方法用溶剂提取，常规硅胶柱色谱分离和葡聚糖凝胶Sephadex LH-20纯化，采用化学方法和现代波谱分析技术（包括IR，HRESIMS，HRSIMS，1D和2DNMR等）鉴定其化学结构。结果从青海产大果大戟根的丙酮提取物中分离得到6个化合物，分别鉴定为：羊毛甾醇（lanosterol，Ⅰ）、巨大戟二萜-20-肉豆蔻酸酯（ingenol-20-myristinate，Ⅱ）、巨大戟二萜-3-肉豆蔻酸酯（ingenol-3-myristinate，Ⅲ）、没食子酸（gallicacid，Ⅳ）、1-O-a-L-阿拉伯糖-（1→6）-β-D-葡萄糖苷-3，7-二甲基-2-烯-7-羟基-辛醇（1-O-a-L-arabinofuranosyl-（1→6）-β-D-glucopyranosyl-3，7-dimethyl-oct-2-en-7-ol，Ⅴ）、1-O-没食子酰葡萄糖苷（1-O-galloyl-β-D-glucose，Ⅵ）。结论巨大戟烷型二萜酯类化合物Ⅱ和Ⅲ为新化合物，其他化合物均为首次从该植物中分离得到，单萜二糖苷类化合物Ⅴ系首次在该属中发现。

Two new diterpenes from Euphorbia kansuensis

Two new lathyrane diterpenes, 3 beta,5 alpha-dihydroxy-15 beta-cinnamonyloxy-14-oxoladiyra-6Z, 12E- diene (1) and 3 beta,5 alpha,20-trihydroxy-15 beta-cinnamoyloxy-14-oxolathyra-6Z, 12E-diene (2), were isolated from the roots of Euphorbia kansuensis. Their structures were determined by spectroscopic methods. (C) 2008 Elsevier B.V. All rights reserved.

Chemical constituents from the whole plant of Euphorbia altotibetic

Four new jatrophane diterpenoids, altotibetin A (1), altotibetin B (2), altotibetin C (3), altotibetin D (4), and nine known compounds, beta-sitosterol, cycloart-23-ene-3beta,25-diol, cycloart-25-ene-3beta,24-diol, lupeol acetate, scopoletin, kaempferol, uracil, uridine, astragalin, and daucosterol have been isolated from the whole plant of Euphorbia altotibetic PAULS. Their structures were established by spectral methods, and the configurations of 1 and 2 were confirmed by X-ray analysis.

葛属(豆科)的分类学修订

本论文对葛属（Pueraria DC.）进行了形态学、解剖学及植物地理学研究，重点分析了小叶、托叶、花序及花的形态变异规律。首次发现葛属生长习性和种皮纹饰特征在组的划分上具有重要的分类学意义，支持前人运用托叶着生方式、花序类型及每节簇生花的数目等特征划分组的观点。首次在光学显微镜下对葛属植物14种1变种叶表皮性状做了较为全面、深入的观察，发现葛属叶表皮细胞的形状、垂周壁的式样以及气孔大小有一定分类学意义，为葛属的分类修订提供了新资料。首次应用电子扫描显微镜观察了葛属10种1变种和2个外类群广西土黄芪Nogra guangxiensis C. F. Wei和琼豆Teyleria koordersii (Backer ex Koord.-Schum.) Backer的种皮纹饰特征，发现葛属的种皮纹饰有网纹型、断棱型、复网纹型和锐棱型等4种类型，他们与托叶的着生方式具有一定的关联性。托叶背着的类群为网纹型，其中采自中国和越南不同居群的山野葛Pueraria montana (Lour.) Merr.种皮次级纹饰有差别，这显示山野葛分化比较活跃。托叶基着的三裂叶野葛P. phaseoloides (Roxb.) Benth.、大花三裂叶野葛P. phaseoloides (Roxb.) Benth. var. javanica (Benth.) Baker、苦葛P. peduncularis (Graham ex Benth.) Benth.以及云南野葛P. yunnanensis Franch.的种皮纹饰为断棱形，小花野葛P. stricta Kurz种皮纹饰为复网纹型，喜玛拉雅葛藤P. wallichii DC.种皮纹饰为锐棱型。依据种皮纹饰推断，喜玛拉雅葛藤最原始，黄毛葛藤P. calycina Franch.最进化，与形态学特征演化方向相吻合。广西土黄芪种皮纹饰为网纹型，琼豆种皮纹饰为复网纹型，表明它们与葛属亲缘关系较近。这与形态学和分子证据相吻合。本文首次运用广义线形模型（GLM）结合地理信息系统（GIS）对葛属现有地理分布、潜在分布及50年后潜在分布进行了分析。所预测的潜在分布范围与观察到的地理分布范围一致，说明对特化的气候忍耐性是限制葛属物种地理分布的主要因素。温度、降水和海拔高度对葛属地理分布限制作用比较大。未来潜在分布预测显示葛属有向南、北扩散的趋势。 作者在研究了四千余份腊叶标本及野外形态考察的基础上，结合叶表皮及种皮纹饰资料，确认葛属分为3组，共19种3变种。其中，对Sect. Breviramulae Maesen ex Z. F. Le & X. Y. Zhu进行了合格发表，运用形态学、解剖学及种皮纹饰资料恢复了云南野葛种的地位，并为其指定了后选模式，P. pulcherrima (Koord.-Schum.) Merr. ex Koord.-Schum.正确的学名为P. sericans Schum.，对4个名称进行了归并。本文还给出了组和种的检索表、葛属各个种的形态描述、地理分布图及模式标本照片。

鹿角蕨化学成分及生物活性的研究

鹿角蕨(Platycerium wallichii Hook.)是鹿角蕨科鹿角蕨属植物，为国家二级保护植物。该植物主要分布在云南西南部盈江县那邦坝，在当地用作跌打药。有关鹿角蕨属的系统关系存在一些假设，关于鹿角蕨属植物化学成分及生物活性的研究未见报道。从鹿角蕨（Platycerium wallichii Hook.）叶95%乙醇提取物中，我们分离得到了七个已知化合物。根据理化常数及波谱数据 (IR、UV、MS及NMR)，其结构分别鉴定为：(I)β一谷甾醇、(II)胡萝卜甙、 (III)2-propenoic acid,3一[(2R, 3S)-2，3-dihydro-2- (4-hydroxy-3-methoxyphenyl) -3- (hydroxymethyl) -7-mnethoxy-5-benzofuranyll -、(Ⅳ)松脂素-4’-0-β -D-葡萄糖甙、(v)松腊素、(Ⅵ)2，5_二羟基苯甲酸甲酯、(Ⅶ)槲皮素3-0-β -半乳糖甙。七个成分均为首次从该种植物中获得。 我们对鹿角蕨(Platvcerium wallichii Hook.)能育叶部分以及基生叶部分的乙醇提取物进行了镇痛试验和抗炎试验，试验表明鹿角蕨（Platvcerium wallichii Hook.）的叶有弱镇痛作用。

绵参和地榆的化学成分研究

本论文由三章组成。第一章为综述，概述了植物中环烯醚萜类化合物的研究进展；第二和第三章为实验论文，分别报道了唇形科药用植物绵参和蔷薇科药用植物地榆的化学成分研究。 第一章概述了植物中环烯醚萜类化合物的研究成果，主要包括结构类型及药理活性等方面。 第二章包括两个部分。第一部分报道了藏药绵参（Eriophyton wallichii Benth）地上部分甲醇提取物的化学成分。采用正、反相硅胶柱层析等各种分离方法，从中共分离出7个化合物，有6个化合物为首次从该植物中分离得到，分别为β-谷甾醇（1），夏至草苦素（marrubiin，2），乌苏酸（3），cimigoside（4），5-deoxyantirrhinoside（5），8-表马钱子酸葡萄糖苷（8-epiloganic acid，6）和apigenin 7-(6''-p-coumaroyl)glucoside（7）。第二部分，采用高效液相色谱－质谱联用技术对绵参地上部分的甲醇提取物进行了分析，通过标准品对照紫、外光谱分析以及多级质谱分析与文献对照鉴定了8个成分，分别是：8-epiloganic acid（Ⅰ），quercitrin 3-glucoside-7-(6''-p-coumaroyl)glucoside（Ⅱ），ajugoside(I) （Ⅲ），chrysoeriol 7-O-E-p-coumaroyl-3-O-b-D-glucoside（Ⅳ），helichrysoside（Ⅴ），生物碱（Ⅵ），apigenin 2,3-dihydrogen-7-(6''-p-coumaroyl) glucoside（Ⅶ），apigenin 7-(6''-p-coumaroyl) glucoside（Ⅷ）。 第三章报道了中药地榆根部乙醇提取物正丁醇相的化学成分，通过正、反相硅胶柱层析等各种分离方法，从中分离得到8个化合物，分别为3,4¢- O-二甲基逆没食子酸（8），3,3¢,4¢-O-三甲基逆没食子酸（9）和3,4¢-O-二甲基逆没食子酸-4-O-b-D-木糖苷（10），19a-羟基-3-O-(a-L-阿拉伯糖)乌苏酸-28-O-b-D-葡萄糖苷（11）， 3b-[(a-L-arabinopyranosyl)oxy]-urs-11,13(18)-dien-28-oic acid b-D- glucopyranosyl ester（13），3-O-a-L-arabinopyranosyl-urs-12,18(19)-dien-28-oic acid b-D-glucopyranosyl ester（14），儿茶素（15），还有一种可能是皂苷11的工作产物（12）。 This dissertation consisted of three chapters. The first chapter elaborated the progress of iridoids occurring in plants. The later two chapters respectively elaborated the chemical constituents of Eriophyton wallichii Benth. and Sanguisorba officinalis L. The first chapter is a review of the research progress of iridoids occurring in plants, which includes their structure and pharmacology. The second chapter consisted of two parts. The first part is about the chemical constituents of methanol extraction from the aerial parts of Eriophyton wallichii Benth. Seven compounds were isolated and identified. Among them, the compounds of marrubiin, ursolic acid, cimigoside, 5-deoxyantirrhinoside, 8-epiloganic acid，apigenin 7-(6''-p-coumaroyl)glucoside were firstly reported in this plant. A HPLC-MSn method was developed for rapid identification of major compounds of Eriophyton wallichii. A total of 8 peaks in the chromatograms were unequivocally determined (peaks 1, 8) or tentatively identified (peaks 2-7) based on the detailed UV and tandem mass spectra analysis. Seven components were identified as 8-epiloganic acid（Ⅰ），Quercitrin 3-glucoside-7-(6''-p-coumaroyl)glucoside（Ⅱ），ajugoside(I)（Ⅲ），Chrysoeriol 7-O-E-p-coumaroyl-3-O-b-D-glucoside（Ⅳ），helichrysoside（Ⅴ），apigenin 2,3-dihydrogen-7-(6''-p-coumaroyl) glucoside（Ⅵ），apigenin 7-(6''-p-coumaroyl) glucoside（Ⅶ）。 The third chapter elaborated the chemical constituents of methanol extraction from Sanguisorba officinalis L, eight compounds were isolated from this plant by repeat column chromatography over silica gel. These compounds were identified as 3,4′-O-dimethylellagic acid, 3,3′,4′-O-trimethylellagic acid, 3,4′-O-dimethylellagic acid-4-O-b-D-xyloside, 3b-O-a-L-arabinopyranosyl-19a- hydroxyl-urs-12-en-28-oic acid 28-b-D-glucopyranoside, 3b-[(a-L-arabinopyranosyl)oxy]-urs-11,13(18)-dien- 28-oic acid b-D-glucopyranosyl ester，3-O-a-L–arabinopyranosyl-urs-12,18(19) -dien-28-oic acid b-D-glucopyranosyl ester, catechin.