云南兔儿风的五环三萜类化学成分研究

The pentacyclic triterpene of Ainsliaea yunnanensis

关键词:  云南兔儿风  化学成分  五环三萜

Key words:  Ainsliaea yunnanensis  chemical constituents  pentacyclic triterpene

摘要:

以采自云南省楚雄自治州楚雄市的云南兔儿风(Ainsliaea yunnanensis)干燥地上部分为研究对象,应用现代色谱手段(硅胶柱色谱、ODS柱色谱、Sephadex LH-20凝胶柱色谱、制备液相及制备薄层色谱等),从云南兔儿风植物中分离单体化合物,运用光谱分析技术(MS、¹H-NMR、¹³C-NMR、DEPT、COSY、HSQC、HMBC、ROSEY)鉴定其化学结构,对云南兔儿风的化学成分进行研究,为兔儿风属植物研究及植物开发利用提供一定的物质基础。结果表明:从云南兔儿风乙醇提取物中共分离得到了11个五环三萜类化合物,分别鉴定为α-香树脂醇乙酸酯(1)、羽扇豆醇乙酸酯(2)、9,12-二烯乌苏烷乙酸酯(3)、α-香树脂酮(4)、羽扇豆烯酮(5)、蛇菰素B(6)、降香萜醇乙酸酯(7)、齐墩果烷-11-羰基-12-烯-3-醇棕榈酸酯(8)、12-烯基白桦脂醇(9)、西米杜鹃醇(10)、二十烷酸羽扇豆醇乙酸酯(11)。其中,化合物1～6,9～11均为首次从该植物中分离得到。通过对云南兔儿风化学分进行深入研究,明确其主要的活性成分,阐明云南兔儿风药用植物中抗炎活性物质基础,为相关的新药科研工作及产品开发提供重要的科学依据。

Abstract:

Plants of Asteraceae are well known for containing biologically active chemical constituents. Within this family,the genus Ainsliaea comprises 70 species,48 of which are indigenous to China. Many Ainsliaea species are used in Chinese folk medicine for various indications. A. yunnanensis,Ainsliaea compositae plant,is born in 1 700-2 700 m above sea level of forests,forest margins,or mountain grass,mainly distributed in Yunnan,Sichuan and other places. And it is used in clinic to treat injuries,fractures,rheumatism bones and muscles pain,indigestion,sores and insect product disease. The latest pharmcological research revealed that A. yunnanensis had wide range of biological activities,such as antioxidant,antitumor,antiinflammatory properties. To explore the material basis of antiinflammatory activities and establish the basis for exploitation and utilization for the future,we had conducted a phytochemical investigation on the EtOH extract of the aerial parts of A. yunnanensis. So far,several sesquiterpenes,triterpenes and flavonoids,had been isolated from this genus. For example,arbutin,friedelin,friedelan-3β-ol,fernenol fom A. frans Champ. 8-α-hydroxy-11α,13-dihydrozaluzanin C,3-O-β-D-glucozaluzanin C from A. fragrans Champ. Acaciin,luteolin,luteolin-7-O-β-D-glucoside,chrysoeriol-7-O-β-D-glucoside,apigenin-7-O-β-D-glucoside from A. bonatii Beauverd. 3,5-dicaffeoylquinic acid and 4,5-dicaffeoylquinic acid from Ainsliaea fragrans Champ. Ainsliaea A,ainsliaea B,zaluzanin C,3-O-(9Z,12Z,15Z-octadecatrienoy1)glycerol,3-0-(9Z,2Z-octadecatrienoy1)glycerol and glueozaluzanin C from A. acerifolia SchBip and A. dissecta Franch Et Sav. Ainsliolide A,ainsliolide B,taraxinc acid,taraxinic acid-14-O-β-D-glueopyranoside from Ainsliaea acerifolia vat subapoda. Three dimeric sesquiterpene lactones were identified as ainsliadimer A,ainsliadimer B,ainsliadimer C from A. macrocephal,and one dimeric sesquiterpene lactone was identified as gochnatiolide A from A. henryi,two triple sesquiterpene lactones(ainsliatriimer A,ainsliatrimer B)from A. fulvioides. In the dissertation,we investigated the chemical constitients of A. yunnanensis systematically,the plant material was collected in Chuxiong Yi Autonomous Prefecture,Yunnan Province,China and identified by Prof. Tan Ceming,plant herbarium of Jiangxi Province. Eleven pentacyclic triterpene compounds were isolated and identified as α-amyrin acetate(1),lupenyl acetate(2),3β-acetoxy-9(11):12-diene-ursan(3),α-amyrenone(4),lupenone(5),balanophorin B(6),bauerenyl acetate(7),3β-hydroxy-11-oxo-olean-12-enyl palmitate(8),lupa-12,20(29)-dien-3β,28-diol(9),simiarenol(10),lup-20(29)-ene-3β-yl eicosanoate(11). These compounds were isolated from A. yunnanensis by silica gel,ODS,Sephadex LH-20,preparative HPLC and preparative TLC and were identified by spectral analysis(MS,¹H-NMR,¹³C-NMR,DEPT,COSY,HSQC,HMBC,ROSEY). Compounds 1-6,9-11 were isolated from A. yunnanensis for the first time. The genus Ainsliaea has been commonly used as crude material of traditional Chinese medicine for a long time,but the study of the genus was sparse,therefore this study would accumulat data for chemical constituents research of the genus.