【作者】 郭远强；

【导师】 李铣；

【作者基本信息】 沈阳药科大学 ， 药物化学， 2004， 博士

【摘要】 南蛇藤(Celastrus orbiculatus Thunb.)系卫矛科南蛇藤属植物，广泛分布于全国各地。南蛇藤主要含有倍半萜类、黄酮类、二萜类等化合物，据文献报道，其果实性平，味甘、微苦，具有镇静、催眠、抗炎、抗癌、昆虫拒食等作用，在我国东北及山东部分地区代替中药合欢花使用，为搞清其有效成分，我们进行了化学和药理学研究。 从南蛇藤干燥果实的乙醇提取物中，通过各种色谱手段(硅胶柱、大孔树脂柱、凝胶柱、RP-HPLC等)分离得到42个化合物，通过理化常数测定、波谱数据分析(UV，NMR，2DNMR和MS等)和化学方法，鉴定了37个化合物的结构，分别为：1β，6α-二乙酰氧基-9α-苯甲酰氧基-β-二氢沉香呋喃(1β，6α-diacetoxy-9α-benzoyloxy-β-dihydroagarofuran，1)，6α，13-二乙酰氧基-1β，8β，9β-三苯甲酰氧基-β-二氢沉香呋喃(6α，13-diacetoxy-1β，8β，9α-tribenzoyloxy-β-dihydroagarofuran，2)，1β，2β，13-三乙酰氧基-9α-苯甲酰氧基-β-二氢沉香呋喃(1β，2p，13-triacetoxy-9α-benzoyloxy-β-dihydroagarofuran，3)，1β-乙酰氧基-9α-肉桂酰氧基-β-二氢沉香呋喃(1β-acetoxy-9α-cinnamoyloxy-β-dihydroagarofuran，4)，1β-乙酰氧基-6α，9α-二苯甲酰氧基-β-二氢沉香呋喃(1β-acetoxy-6α，9α-dibenzoyloxy-β-dihydroagarofuran，5)，1β，6α，8β-三乙酰氧基-9α-苯甲酰氧基-β-二氢沉香呋喃(1β，6α，8β-triaceloxy-9α-benzoyloxy-β-dihydroagarofuran，6)，1β，6α-二乙酰氧基-9β-苯甲酰氧基-8β-肉桂酰氧-β-二氢沉香呋喃(1β，6α-diacetoxy-9β-benzoyloxy-8β-cinnamoyloxy-β-dihydroagarofuran，7)，1β，2β-二乙酰氧基-9α-肉桂酰氧基-β-二氢沉香呋喃(1β，2β-diacetoxy-9α-cinnamoyloxy-β-dihydroagarofuran，8)，1β，2β，6α-三乙酰氧基-9α-苯甲酰氧基-β-二氢沉香呋喃(1β，2β，6α-triacetoxy-9β-benzoyloxy-β-dihydroagarofuran，9)，6α-乙酰氧基-1β，8β，9β-三苯甲酰氧基-β-二氢沉香呋喃(6α-acetoxy-1β，8β，9β-tribenzoyloxy-β-dihydroagarofuran，10)，1β，6α，13-三乙酰氧基-9α-苯甲酰氧基-β-二氢沉香呋喃(1β，6α，13-triacetoxy-9α-benzoyloxy-β-dihydroagarofuran，11)，1β，6α-二乙酰氧基-8β，9β-二苯甲酰氧基-β-二氢沉香呋喃(1β，6α-diacetox-y-8β，9β-dibenzoyloxy-β-dihydroagarofuran，12)，6α-乙酰氧基-9β-苯甲酰氧基-1β-肉桂酰氧基-8β-丁酰氧基-β-二氢沉香呋喃(6α-acetoxy-9β-benzoyloxy-1β-cinnamoyloxy-8β-butanoyloxy-β-dihydroagarofuran，13)，1β，2β-二乙酰氧基-6α-苯甲酰氧基-9α-肉桂酰氧基-β-二氢沉香呋喃(1β，2β-diacetoxy-6α-benzoyloxy-9α-cinnamoyloxy-β-dihydroagarofuran，14)，1β，8β-二乙酰氧基-9β-肉桂酰氧基-2β-己酰氧基-β-二氢沉香吠喃(lp，sp一diaeeto称一gp一einnamoyloxy一Zp一hexan叮Ioxy一p一dihydroagarofuran，15)，6a一乙酞氧基一gp一苯甲酞氧基一lp一肉桂酞氧基一sp一(2一甲基丁酞氧基卜p一二氢沉香吠喃(6a心ceto科一gp一benzoylo拟一lp一innamoyloxy一sp一(2一methylbutan叮10材)一p刁ihydroagarofuran，16)，lp，Zp， sa-三乙酞氧基一ga一肉桂酞氧基一p一二氢沉香峡喃(lp，Zp，sa一riacetoXy一ga-cinnamoyfoxy一p一hydroagarofuran 17)，6a一乙酞氧基一lp，gp一二苯甲酞氧基一sp一轻基一p一二氢沉香吠喃(6。一acetoxy一lp，9卜dibenz叮10翔一8卜hydro秒一p刁ihydro鳃aro九ran，18)，lp，6a一二乙酞氧基一gp一苯甲酞氧基一sp一轻基一p一二氢沉香峡喃(lp，6a一diacetoxy一gp一benzoyloxy-8卜hydroxy一p一dihydroagarofuran，19)，lp，Zp，6a一三乙酸氧基一ga-肉桂酞氧基一p一二氢沉香映喃(lp，Zp，6a一triaceto材一ga一einnamoylo翔一p一dihydroagarofuran，20)，lp，Zp，6a，13一四乙酞氧基一ga一肉桂酸氧基一p一二氢沉香吠喃(lp，Zp，6a，13一tetraaeetoxy一ga一cinnamoyloxy-卜dihydroagarofuran，21)，6a一乙酞氧基一lp，sp一二苯甲酞氧基一gp一轻基一p一二氢沉香吠喃(6a一aeeto砂一lp，8卜dibenzoylo林一gp一hydro材一p一dihydroagarofuran，22)，山奈酚(kaempfero!，23)，棚皮素(quercetin，24)，山奈酚一7一o-a一L一鼠李糖普(kaempferol一7一o-a一L一thamnoside，25)，榭皮素一7一O一a一L一鼠李糖营(quercetin一7一o-a一L一rhamnoside，26)，LIJ奈酚一3，7一o-a一L一二鼠李糖营(kaempferol一3，7一o-a一L一dirhamnoside，27)，LlJ蔡酚一7一。一a一L一鼠李糖基一3一o-p一D一葡萄糖基(l~4卜a一L一鼠李糖昔(kaempferol一7一O一a一L一rhamnosyl一3一O-卜D一glueopyranoyl(l一4卜a·L一dirhamnoside，28)，苯甲酸( benzoie acid，29)，2一经基苯甲酸(2一ydroxy benzoie acid，30)，3，4一二轻基苯甲酸(3，4一dihydroxy benzoie aeid 31)，4一经基苯甲醛(4一hydro称benZaldehyde，32)，香草酸(vanillie acid，33)，(65，7aR}6一轻基一4，4，7a一三甲基一5，6，7，7a-四氢?更多还原

【Abstract】 Celastrus orbiculatus Thunb. is a member of family Celastraceae. It is a traditional herbal medicine which is widely distributed in China. The constituents of Celastrus orbiculatus are complicated, such as sesquiterpenes, flavonoids, tripenes et al. Its fruits had activities in tranquilization, hypnogenesis, antiinflammation, antitumor, antifeedant, and had been used as the substitute of flowers of Albizia julibrissin. In order to find the active constituents, the systemic studies on its chemistry and pharmacology were carried out.42 constituents were isolated from the fruits of Celastrus orbiculatus by using open-column chromatograph, and PHPLC methods et al. On the basis of analysis of UV, NMR, MS data and physico-chemical constants, the structures of 37 compounds were identified as following: 1β, 6a-diacetoxy-9a-benzoyloxy-p-dihydroagarofuran (1), 6a, 13-diacetoxy-1β, 8β, 9a-tribenzoyloxy-p-dihydroagarofuran (2) , 1β, 2β, 13-diacetoxy-9β-benzoyloxy-β-dihydro-agarofuran (3), lβ-acetoxy-9a-cinnamoyloxy-p-dihydroagarofuran (4), 1 B-acetoxy-6a, 9a-dibenzoyloxy-β-dihydroagarofuran (5), 1β, 6a 8B-triacetoxy-9a-benzoyloxy-β-dihydroagaro-furan (6), 1β, 6a-diacetoxy-9β-benzoyloxy-8β-cinnamoyloxy-p-dihydroagarofuran (7), la, 2a-diacetoxy-9β-cinnamoyloxy-β-dihydroagarofuran (8), 1β, 2β, 6a-triacetoxy- 9β-benzoyloxy-β-dihydroagarofunan (9), 6a-acetoxy-1β, 8β, 9β-tribenzoyloxy-β- dihydroagarofuran (10), 1B, 6a,13-triacetoxy-9a-benzoyloxy-p-dihydroagarofuran (11), 1β, 6a-diacetoxy-8β, 9β-dibenzoyloxy-β-dihydroagarofuran (12), 6a-acetoxy-9β-benzoyloxy-1β-cinnamoyloxy-8p-butanoyloxy-β-dihydroagarofuran (13), 1β, 2β-diacetoxy-6a-benzoyloxy-9a-cinnamoyloxy-p-dihydroagaro-furan (14), 1β, 8β-diacetoxy-9β-cinnamoyloxy-2β-hexanoyloxy-p-dihydroagarofiiran (15), 6a-acetoxy-9p-benzoyloxy-lp-cinnamoyloxy-8β-(2-methylbutanoyloxy)-β-dihydroagarofuran (16), la, 2a, 8p-triacetoxy-9p-cinnamoyloxy-8β-(2-methylbutanoyloxy)-β-dihydroagarofuran (17), 6a-acetoxy-lβ, 9β-dibenzoyloxy-8p-hydroxy-β-dihydroagarofuran (18), iβ, 2β, 6a-triacetoxy-9β-cinnamoyloxy-p-dihydroagarofuran (19),1β, 2β, 6a-triacetoxy-9β-cinnamoyloxy-β-dihydroagarofuran (20), 1β, 2β, 6a, 13-tetraacetoxy-9p-cinnamoyloxy-p-dihydroagarofuran (21), 6a-acetoxy-1β, 8β-dibenzoyloxy-9β-hydroxy-p-dihydroagarofuran (22), kaempferol (23), quercetin (24), kaempferol-7-O-a-L-rhamnoside (25), quercetin-7-O-a-L-rhamnoside (26) , kaempferol-3,7-O-a-L-dirhamnoside (27), kaempferol-7-O-a-L-rhamnosyl-3-O-β-D-glucopyranoyl(1-4)-a-L- dirhamnoside (28), benzoic acid (29), 2-hydroxy benzoicacid, (30), 3, 4-dihydroxy benzoic acid (31), 4-hydroxy benzaldehyde (32), vanillic acid (33), (6S, 7aR)-6-hydroxy-4, 4, 7a-trimethyl-5, 6, 7, 7a-tetradihydrobenzofuran- 2(4H)-one (34), 3, 4-dihydro-3-oxo-4-benzyl-lH-pyrrolo[2, l-c][1, 4]oxazine-6-carboxaldehyde (35), p-sitosterol (36), daucosterol (37).Among them, compound 2 , 3, 13, 15, 16, 20, 21 and 22 are new compounds; compound 35 is a new natural product; compounds 28~34 were first isolated from this genus.A review on the type of structures, the spectral characters and so on of p-dihydroagarofuran was given based on the literatures and our research work.The pharmacological experiments showed that the extract of fruits of C. orbiculatus had no effects on spontaneous movements of mice, so the use of fruits should be discussed further instead ofAlbiziajulibrissin flowers.The experiments inhibiting the proliferation of tumor cells indicated that p-dihydroagarofuran sesquiterpene esters, isolated from the fruits of Celastrus orbiculatus, had obvious activity of inhibiting the proliferation in Hela and A375-S2 cells at the concentration of 40ug/ml.In vitro experiments of anti-inflammation, the ethanol extract of the fruits of Celastrus orbiculatus suppressed the NF-kB activation and NO production and the active part should be the petroleum ether partition of fruits extract. Extended research showed that the main chemical constituents of petroleum ether part, β-dihydroagarofuran se更多还原