离舌橐吾中艾里莫酚烷型倍半萜类化学成分的研究

为分析菊科橐吾属植物离舌橐吾Ligularia veitchiana(Hemsl.)Greenm中艾里莫酚烷型倍半萜类的化学成分,并对其进行抗肿瘤活性研究,实验综合运用硅胶柱色谱、反相硅胶柱色谱以及制备型高效液相等色谱方法,从其根茎的95%乙醇提取物的乙酸乙酯部位中分离得到了13个艾里莫酚烷型倍半萜类化合物,根据化合物的理化性质及其波谱学数据鉴定为:eremophilenolide(1),eremophila-7(11),9-dien-8-one(2),eremophil-6-en-11-ol(3),8-oxo-eremophil-6-en-11-one(4),(6α,8α)-6-hydroxyeremophil-7(11)-en-12,8-olide(5),8β-hydroxyeremophil-7(11)-en-12,8α-olide(6),6β-hydroxy-8α-methoxyeremophil-7(11)-12,8β-olide(7),2α-hydroxyeremophil-11-en-9-one(8),6β-methoxy-8β-hydroxyeremophil-7(11)-en-12,8α-olide(9),6β-hydroxyeremophil-7(11)-en-12,8β-olide(10),6β-hydroxy-8β-methoxyeremophil-7(11)-12,8α-olide(11), 6β,8β-dihydroxyeremophil-7(11)-en-12,8α-olide(12)和6β,8α-dihydroxyeremophil-7(11)-en-12,8β-olide(13)。其中,化合物5和10、7和11～13为三对非对映异构体。除化合物3和5外,所有化合物均为首次从该植物中分离得到。运用MTT法对所有化合物进行体外抗肿瘤细胞活性的筛选,结果表明其对胃癌细胞HGC-27和宫颈癌细胞Caski均未显示细胞毒作用。     

灵芝子实体中的羊毛脂烷型灵芝酸酯类成分研究

目的系统研究灵芝子实体中的羊毛脂烷型灵芝酸酯类成分。方法通过氯仿对盐酸酸化的灵芝子实体提取物中的羊毛脂烷型三萜酸类成分进行萃取,结合硅胶柱层析、中压柱层析(RP C18色谱柱)、制备型HPLC(RP C18色谱柱)对提取物中的三萜酸酯类化学成分进行系统的分离、纯化。通过UV、ESIMS、HRESI-MS、1 H-NMR、13C-NMR、HSQC、HMBC、NOESY等波谱学手段结合文献数据对制备得到的三萜类单体成分进行准确的结构测定。结果从灵芝子实体的氯仿提取物中共分离鉴定了10个羊毛脂烷型灵芝酸酯类成分,分别为:(1)Ganoderic acid AP,(2)Methyl Ganoderate G,(3)Ganoderic acid H,(4)12β-Hydroxy-3,7,11,15,23-pentaoxo-5α-lanost-8-en-26-oic acid,(5)Ganoderic acid K,(6)Ganoderenic acid B,(7)Lucienic acid A,(8)Lucidenic acid B,(9)20(21)-Dehydrolucidenic acid A,(10)Lucidone D。结论灵芝子实体中极性较小的化学成分主要为羊毛脂烷型三萜及其降碳衍生物,该类成分多具有羧基或羧酸酯官能团,既而也称灵芝酸类,本文共分离鉴定了10个该系列成分,其中化合物1为新化合物。     

金樱根化学成分的研究

金樱根为三金片的主要成分,但目前对于金樱根的化学成分和药理作用研究甚少。为了阐明金樱根的物质基础和生物活性,该研究采用硅胶、Sephadex LH-20、MCI gel CHP 20P等柱色谱以及HPLC半制备等方法,对金樱根(Rosa laevigata)的化学成分进行研究。结果表明:从中共分离得到9个化合物,经过波谱数据分析结合文献对照分别鉴定为儿茶素(1),表儿茶素(2),rosamultin(3),sericoside(4),2α,3α,19α,23-tetrahydroxy-urs-12-en-28-oic acid-3-O-β-D-glucopyranosyl ester(5),kaji-ichigoside F1(6),β-D-Glucopyranosyl 3β,19α-dihydroxy-2-oxo-urs-12-en-28-oate(7),胡萝卜苷(8),β-谷甾醇(9),其中化合物2、4、5、7为首次从该植物中分离得到。该研究结果为金樱根在功能医药领域的开发利用提供了理论依据。     

小花琉璃草化学成分的研究

从小花琉璃草(cynoglossum lanceolatym Forsk.)全草的石油醚提取物中分离到5个化合物,用波谱等方法鉴定为:十六碳酸甲酯(Hexadecanoic acid,methyl ester)、β-谷甾醇(β-sitosterol)、5α,豆甾烷-3,6-二酮(5α,stigmastane-3,6-dione)、6β-羟基-豆甾-4-烯-3酮(6-β-hydroxy-stigmasta-4-en-3-one)和胡萝卜甙(daucosterol)。     

马缨杜鹃茎的化学成分研究

利用各种色谱技术从马缨杜鹃(Rhododendron delavayi Franch.)茎中分离得到10个化合物。通过波谱学方法鉴定为异鼠李素(1),nectandrin B(2),resveratrol-3-O-β-D-glucoside(3),lysidiside N(4),19α-hydroxyasiatic acid(5),白桦脂酸(6),3β-hydroxylup-12-en-28-oic-acid(7),obtusalin(8),methyl 2,4-dihydroxy-6-methylbenzoate(9),2,5-dihydroxy-3-methoxytoluene(10)。化合物2～9为首次从该种植物中分离得到。     

南海疏枝刺柳珊瑚中甾醇类化合物的研究

本文对采自海南三亚海域的疏枝刺柳珊瑚(Echinogorgia pseudossapo)化学成分进行研究,分离到11个甾醇类化合物。经波谱数据分析,分别鉴定为cholest-5-en-3β-ol(1),24-methylene-cholest-4-ene-3β,6β-diol(2),24-norcholesta-22-en-3β-ol(3),acanthovagasteroid A(4),calicoferol E(5),calicoferol F(6),6-hydroxy-cholest-4-ene-3-one(7),echinoflorasterol(8),echissaposterol(9),24-methylcholest-5-en-3β,7α-diol(10)和24-methylcholest-5,22(E)-dien-3β,7α-diol(11)。除化合物8外,其余化合物均首次从该种海洋动物中分离得到。     

木奶果茎叶的化学成分研究

采用常压柱色谱和重结晶相结合的分离方法,从木奶果的茎叶提取物的乙酸乙酯部分中分离得到8个化合物,通过波谱方法及与已知样品对照的手段鉴定它们为(2S,3S,4R)-2-[(2R)-2-hydroxytetracosanoyl-amino]-1,3,4-octadecanetriol(1),Aralia cerebroside(2),(24S)-24-ethylcholesta-3β,5α,6β-triol(3),Stigmast-4-en-6β-ol-3-one(4),7-oxo-β-sitosterol(5),7α-methoxy-sigmast-5-en-3β-ol(6),β-sitosterol(7),daucosterol(8)。化合物1-6为首次从该种植物中发现的。     

驼绒藜化学成分研究

从驼绒藜(Ceratoides latens)乙醇提取物中分离得到9个化合物,经波谱分析将它们分别鉴定为香草酸(vanilic acid)(1),乙酰香子兰酮(acetovanillon)(2),三达右松脂-15-烯-8β,12β-二醇(sandaracopimar-15-en-8β,12β-diol)(3),5,7,3’,4’-四甲基槲皮素(5,7,3’,4’-tetramethyl quercitin)(4),小麦黄酮(tricin)(5),丁香亭3-O-β-D-葡萄糖苷(syringetin-3-O-β-D-glycopyranoside)(6),β-谷甾醇(β-sitosterol)(7),胡萝卜苷(daucosterol)(8)和豆甾醇(stigmasterol)(9)。这些化合物均为首次从该植物中分离得到。     

云南割舌树的化学成分

从云南割舌树（Walsura yunnanensis C.Y.Wu.)树皮的乙醇提取物中分离鉴定了12个化合物,它们分别是walsurol(1),tocopherol(2),sitoindoside Ⅰ（3）,3β-stigmast-5-en-3-yl-β-D-xylopyranoside(4),stigmast-4-en-6β-ol-3-one(5),7-oxositosterol(6),3β-hydroxy-5α,8α-epidioxyergosta-6,22-diene(7),(-)epicatechin(8),3,5-dihydroxy-4-methoxylphenylethanol(9),间三甲氧基苯,（β－谷甾醇和胡萝卜甙,新化合物1命名为割舌醇（walsurol)。     

肋果茶中的萜类化学成分研究

从肋果茶(Sladenia celastrifolia)95％乙醇提取物的乙酸乙酯部位中分离得到15个萜类化合物,经波谱学方法分别鉴定为sladeniafolin A(1),grasshopper ketone (2),(3S,5R,6S,7E,9R) -7-megastigmene-3,6,9-triol (3),hedytriol (4),(3S,5R,6R,7E,9R) -3,5,6,9-tetrahydroxy-7-megastigmene(5),1′S*,4′R*-8-(4′-hydroxy-2′,6′,6′-trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien -2-one (6),2α,3α,19α,23-tetrahydroxyurs-12-en-28-oic acid (7),2α,3β,19α,23-tetrahydroxyurs-12-en-28-oic acid(8),pomolic acid(9),3-O-acetyl pomolic acid(10),ursaldehyde (11),camarolide (12),3β-hydroxyurs-11-en-13β(28) -olide (13),3β-hydroxy -11α,12α-epoxy-urs-13β,28-olide (14)和28-0-β-D-glucopyranosyl euscaphic acid (15).以上化合物均首次从该植物中分离得到,其中1为新的C9裂环烯醚萜.     

Selective cholinesterase inhibition by lanostane triterpenes from fruiting bodies of Ganoderma lucidum

Two new lanostane triterpenes, named methyl ganoderate A acetonide (1) and n-butyl ganoderate H (2), were isolated from the fruiting bodies of Ganoderma lucidum together with 16 known compounds (3-18). Extensive spectroscopic and chemical studies established the structures of these compounds as methyl 7β,15α-isopropylidenedioxy-3,11,23-trioxo-5α-lanost-8-en-26-oate (1) and n-butyl 12β-acetoxy-3β-hydroxy-7,11,15,23-tetraoxo-5α-lanost-8-en-26-oate (2). Because new compounds exhibiting specific anti-acetylcholinesterase activity are being sought as possible drug candidates for the treatment of Alzheimer's and related neurodegenerative diseases, compounds 1-18 were examined for their inhibitory activities against acetylcholinesterase and butyrylcholinesterase. All of the compounds exhibited moderate acetylcholinesterase-inhibitory activity, with IC(50) values ranging from 9.40 to 31.03μM. In contrast, none of the compounds except lucidadiol (13) and lucidenic acid N (14) exhibited butyrylcholinesterase-inhibitory activity at concentrations up to 200μM. These results indicate that these lanostane triterpenes are preferential inhibitors of acetylcholinesterase and may be suitable drug candidates.     

Lanostane triterpenoids and sterols from Antrodia camphorata

Four lanostane triterpenes, 3,7,11-trioxo-5α-lanosta-8,24(E)-dien-26-oic acid, methyl 11α-3,7-dioxo-5α-lanosta-8,24(E)-dien-26-oate, methyl 3,7,11,12,15,23-hexaoxo-5α-lanost-8-en-26-oate, and ethyl 3,7,11,12,15,23-hexaoxo-5α-lanost-8-en-26-oate, two sterols, (14α,22E)-14-hydroxyergosta-7,22-diene-3,6-dione and a steroid named as camphosterol A were isolated from a mixture of fruiting bodies and mycelia of solid cultures of Antrodia camphorata. The ¹H and ¹³C NMR spectra of all compounds were fully assigned using a combination of 2D NMR experiments, including COSY, HMQC, HMBC and NOESY sequences. Six compounds were evaluated for cytotoxicity against several human tumor cell lines, all of which has moderate activity.     

Structures of the Metabolites from Steviol Methyl Ester by Gibberella fujikuroi

Steviol methyl ester (methyl ent-13-hydroxykaur-16-en-19-oate)* was converted into five new metabolites together with a known compound, methyl ent-7α,13-dihydroxykaur-16-en-19-oate, by Gibberella fujikuroi in the presence of a plant growth retardant. The structures of these new metabolites were elucidated to be methyl ent-7β,13-dihydroxykaur-16-en-19-oate, methyl ent-11α,13-dihydroxykaur-16-en-19-oate, methyl ent-7β,11α,13-trihydroxykaur-16-en-19-oate, methyl ent-11α, 13,15β-trihydroxykaur-16-en-19-oate and methyl ent-13,15β-dihydroxy-11-oxokaur-16-en-19-oate mainly by spectroscopic analyses.     

New Bitter C27 and C30 Terpenoids from the Fungus Ganoderma lucidum (Reishi)

Four new bitter terpenoids, lucidenic acids A (1), B (2), C (3) and ganoderic acid C (5), were isolated from the fruiting bodies of Ganoderma lucidum, together with the known bitter ganoderic acid B (4). On the basis of spectroscopic data and chemical conversion, their structures were determined to be 7β-hydroxy-4,4,14α-trimethyl-3,11,15-trioxo-5α-chol-8-en-24-oic acid, 7β,12β-dihydroxy-4,4,14α-trimethyl-3,11,15-trioxo-5α-chol-8-en-24-oic acid, 3β,7β,12β-trihydroxy-4,4,14α-trimethyl-11,15-dioxo-5α-chol-8-en-24-oic acid and 7β-hydroxy-3,11,15,23-tetraoxo-5α-lanost- 8-en-26-oic acid, respectively.     

Constituents of various wood-rotting basidiomycetes

Phytochemical investigation of n-hexane and methanol extracts of fruiting bodies of the wood-rotting fungi Fomitopsis pinicola. Ganoderma lipsiense, Fomes fomentarius and Gloeophyllum odoratum led to the isolation and identification of several triterpene derivatives and some aromatic compounds derived from lignin. These are the new natural products, namely, pinicolic acid E (16alpha-hydroxy-3-oxolanosta-8,24-dien-21-oic acid) and pinicolol C (3-oxolanosta-7,9(11),24-trien-15alpha,21-diol) from the crust of F. pinicola, ganoderenic acid D [(E)-7beta-hydroxy-3,11,15,23-tetraoxolanosta-8,20(22)-di en-26-oic acid] and ganoderic acid N (7beta,20-dihydroxy-3,11,15,23-tetraoxolanost-8-en-26-oic acid) from G. lipsiense and ergosterol peroxide (5alpha,8alpha-epi-dioxyergost-6-en-3beta-ol) as well as ergost-7-en-3-one from F. fomentarius. From G. odoratum, dehydroeburicoic acid [24-methylene-3-oxolanosta-7,9(11)-dien-21-oic acid], the dimethylacetal of 4,4,14alpha-trimethyl-24-oxo-5alpha-chol-8-en-21-oic acid and some aromatic compounds, of which 1-(4'-methoxyphenyl)-1,2-ethandiol is a new natural product, were isolated. Furthermore, a complete set of 13C NMR data of the steryl esters 3beta-linoleyloxyergosta-7,24(28)-diene, 3beta-linoleyloxyergosta-7,24-diene and 3beta-linoleyloxyergost-7-ene, which could be identified as a mixture in all investigated fungi, could be recorded. It was proved by HPLC and TLC investigations, that the crust on top of the fruiting bodies of F. pinicola consists of lanostane derivatives.     

A new nortriterpenoid from the fruiting bodies of Ganoderma tropicum

Ganoderma tropicum has been widely used by the local folks for coronary heart disease treatment, liver protection, and sleep aid. In order to discover natural active components and tap the medical potential of G. tropicum, the chemical investigation of its fruiting bodies was carried out. This study led to the isolation of a new nortriterpenoid named 26-nor-11,23-dioxo-5α-lanost-8-en-3β,7β,15α,25-tetrol (1) and a known nortriterpenoid lucidone D (2). The structure of the new nortriterpenoid was elucidated by spectroscopic techniques including UV, IR, MS, 1D and 2D NMR spectroscopy.     

Biotransformation of methyl cholate by Aspergillus niger

Biotransformation of methyl cholate using Aspergillus niger was investigated. This led to the isolation of two derivatives: methyl 3α,7α,12α,15β-tetrahydroxy-5β-cholan-24-oate identified as a new compound, and a known compound methyl 3α,12α-dihydroxy-7-oxo-5β-cholan-24-oate. The structure elucidation of the new compound was achieved using 1D and 2D NMR, MS and X-ray diffraction.     

Synthesis of homoursodeoxycholic acid and [11,12-3H]homoursodeoxycholic acid

Homoursodeoxycholic acid and [11,12-³H]homoursodeoxycholic acid were synthesized from ursodeoxycholic acid and homocholic acid, respectively. Ursodeoxycholic acid (Ia) was converted to 3α,7β-diformoxy-5β-cholan-24-oic acid (Ib) using formic acid. Reaction of the diformoxy derivative (Ib) with thionyl chloride yielded the acid chloride (II) which was treated with diazomethane to produce 3α,7β-diformoxy-25-diazo-25-homo-5β-cholan-24-one (III). Homoursodeoxycholic acid (IV) was formed from the diazoketone (III) by means of the Wolff rearrangement of the Arndt-Eistert synthesis.N-Bromosuccinimide oxidation of homocholic acid (V), which was prepared from cholic acid by the same procedure described above, afforded 3α,12α-dihydroxy-7-oxo-25-homo-5β-cholan-25-oic acid (VI). Reduction of the 7-ketohomodeoxycholic acid (VI) with sodium in 1-propanol gave 3α,7β,12α-trihydroxy-25-homo-5β-cholan-25-oic acid (VII). The methyl ester of 7-epihomocholic acid (VII) was partially acetylated to give methyl 3α,7β-diacetoxy-12α-hydroxy-25-homo-5β-cholan-25-oate (VIII) using a mixture of acetic anhydride, pyridine and benzene. Dehydration of the diacetoxy derivative (VIII) with phosphorus oxychloride yielded methyl 3α,7β-diacetoxy-25-homo-5β-chol-11-en-25-oate (IX). Reduction of the unsaturated ester (IX) with tritium gas in the presence of platinum oxide catalyst followed by alkaline hydrolysis gave [11,12-³H]homoursodeoxycholic acid.     

Tirucallane triterpenes from the roots of Ozoroa insignis

Eight tirucallane triterpenes, methyl 3alpha,24S-dihydroxytirucalla-8,25-dien-21-oate (2), methyl 3alpha-hydroxy-24-oxotirucalla-8,25-dien-21-oate (3), methyl 3alpha-hydroxy-25,26,27-trinor-24-oxotirucall-8-en-21-oate (4), 3alpha,25-dihydroxy-24-(2-hydroxyethyl)-tirucall-8-en-21-oic acid (5), 3alpha,24S,25-trihydroxytirucall-8-en-21-oic acid (6), 3alpha,24R,25-trihydroxytirucall-8-en-21-oic acid (7), 3alpha,25-dihydroxytirucall-8-en-21-oic acid (8), and methyl 3alpha,25-dihydroxytirucall-8-en-21-oate (9), together with alpha-elemolic acid methyl ester (1), were isolated from the roots of Ozoroa insignis. Their structures were elucidated on the basis of spectroscopic evidence.     

高等真菌黑虎掌子实体的化学成分

黑虎掌 (Ｓａｒｃｏｄｏｎａｓｐｒａｔｕｍ (Ｂｅｒｋ .)Ｓ .Ｉｔｏ) ,又名香茸 ,是一种美味食用菌。近年来发现该属Ｓ .ｓｃａｂｒｏ ｓｕｓ (Ｆｒ.)Ｐ .Ｋａｒｓｔ.中含有对神经生长因子 (ＮＧＦ)的合成具有诱导作用的生物活性二萜 (Ｏｈｔ等 ,1998)。作为“高等真菌生物活性代谢产物研究”的一部分 ,我们对采自云南武定的样品进行了化学分析。从黑虎掌的新鲜子实体中分得 15个化合物。它们分别为ｃｅｒｅｂｒｏｓｉｄｅＢ (1) (12 0ｍｇ) ,阿洛酮糖腺苷(2 ) (12ｍｇ) ,三磷酸尿苷 (3) (7ｍｇ) ,尿嘧啶 (4 ) (12ｍｇ) ,腺嘌呤 (5 ) (8ｍ…