蒲公英中两个黄酮甙的分离鉴定

5　K azuyuki Hidaka,Miyoko Ito,Y oko Matsuda,et al.A Triter2 pene and Saponin from Roots of Ilex pubescens.Phytochem2

istry,1987,26(7):2023

　　致谢　本研究得到日本安寿元制药株式会社水野昌典社长和日本岐阜药科大学水野瑞夫原校长的大力支持。

1998203217收稿

蒲公英中两个黄酮甙的分离鉴定

凌云　鲍燕燕　郭秀芳

(海军总医院药剂科　北京100037)

徐杨　蔡少青　郑俊华

(北京医科大学药学院　北京100083)

　　摘要　目的:研究蒲公英的化学成分。方法:溶剂提取和柱层析进行分离,根据化合物理化性质和光谱数据鉴定其结构。结果:分离并鉴定了2个黄酮甙,分别为槲皮素232O2葡萄糖甙和槲皮素232O2β2半乳糖甙。结论:均首次从该种植物中分得。

关键词　蒲公英　黄酮

　　我们曾报道蒲公英含有抗菌的咖啡酸和绿原酸[1]及黄酮类成分[2],现又从该植物中分离出2个黄酮甙,分别鉴定为槲皮素232O2葡萄糖甙和槲皮素232O2β2半乳糖甙。

1　仪器与材料

X24显微熔点仪(未校正),Perkin2Elmer 983G红外光谱仪,岛津260分光光度计,Vari2 an500MHz核磁共振仪,MS250质谱仪。

柱层析硅胶H和薄层层析用硅胶GF2254 (青岛海洋化工厂),柱层析用聚酰胺(200目,江苏省无锡县电化厂),聚酰胺薄膜(浙江黄岩四青化工厂)。薄层层析在UV254或UV365紫外灯下观察;1%AlCl3乙醇,10%H2SO4乙醇显色。蒲公英采自呼和浩特市内(连根挖起,晒干),作者鉴定为Tarax acum mongolicum Hand.2Mazz.的干燥全草。

2　提取与分离

蒲公英干燥全草2kg,95%乙醇温浸3次,过滤合并。滤液减压回收得浸膏。浸膏混悬于500ml水中,分别用石油醚、乙酸乙酯和正丁醇进行萃取,各部分经减压浓缩。乙酸乙酯部分硅胶低压柱层析,氯仿2甲醇梯度洗脱,其中氯仿2甲醇(1∶1)洗脱部分用聚酰胺层析,氯仿2甲醇反复柱层析得化合物Ⅰ,Ⅱ。

3　鉴定

化合物Ⅰ　黄色粉末(甲醇),mp240～242℃,HCl2Mg,Molish反应均阳性,薄层层析AlCl3乙醇显色后黄色加深。IR(K Br)cm-1: 3256(OH),2920(CH),1650(C O),1660, 1551,1501(Ar)。UVλmax nm:358(Ⅰ带),256 (Ⅱ带),266(肩峰),示B环有3′,4′取代。1HNMR(DMSO2d6)δ:6.21(1H,d,J= 2.0Hz,62H),6.41(1H,d,J=2.0Hz,82H),示A环5,7取代;6.84(1H,d,J=7.0Hz,5′2H), 7.57(1H,d,J=2.0Hz,2′2H),7.58(1H,dd,J= 7.0,2.0Hz,6′2H),示B环1,3,4取代;5.46 (1H,d,J=7.5Hz,1″2H),为糖上端基质子;

3.23(6H,m,2″,3″,4″,5″,6″2H),为糖环上氢。EI2MS m/z:302(M-glc),153(A1+H),137 (B2)。Ⅰ酸水解后纸层析,糖为葡萄糖。与文献对照[3],确定为槲皮素232O2葡萄糖甙,即异槲皮甙(isoquercitrin)。

化合物Ⅱ　黄色粉末(95%乙醇),mp223～225℃,HCl2Mg,Molish反应均阳性,薄层层析AlCl3乙醇显色后黄色加深。IR(K Br) cm-1:3341(OH),2919(CH),1656(C O), 1601,1557,1491(Ar)。UVλmax nm:358(Ⅰ带), 256(Ⅱ带),266(肩峰),示B环有3′,4′取代。1HNMR(DMSO2d6)δ:6.20(1H,d,J= 1.5Hz,62H),6.43(1H,d,J=1.5Hz,82H),示A环5,7取代;6.82(1H,d,J=7.0Hz,5′2H), 7.56(1H,d,J=2.0Hz,2′2H),7.58(1H,dd,J= 7.0Hz,J=2.0Hz,6′2H),示B环ABX系统;

5.28(1H,d,J=7.5Hz,1″2H),为糖上端基氢,示β键。结合H2H COSY,3.53(1H,dd,J= 7.5,9.2Hz,2″2H),3.35(1H,dd,J=3.5, 9.2Hz,3″2H),3.(1H,d,J=3.5Hz,4″2H),3.42(1H,t,J=

6.2,10.2Hz,5″2H),3.31(1H, dd,J=6.2,10.2Hz,6″2Ha),3.26(1H,dd,J= 6.2,10.2Hz,6″2Hb),示4″,5″位的J值为零,其两面角接近90℃表明4″2H处于e位,因此糖为半乳糖。EI2MS m/z:302(M-Gul),273(M-Gul-CO),153(A1+H),137(B2)。Ⅱ酸水解后纸层析,糖为半乳糖。确定为槲皮素232O2β2半乳糖甙,即金丝桃甙(hyperin)。

4　参考文献

1　凌云,鲍燕燕,朱莉莉,等.蒲公英化学成分的研究.中国药学杂志,1997,32(10):584

2　凌云,张雅林,蔡少青,等.碱地蒲公英黄酮类和甾醇类成分的研究.中国药物化学杂志,1998,8(1):46

3　中国科学院上海药物研究所植物室.黄酮体化合物鉴定手册.北京:科学出版社,1981.485

1998204228收稿

月腺大戟化学成分研究

孙晓飞　(山西医科大学药学系　太原030001)

王淑萍　(山西省肿瘤医院　太原030013)

郑泽荣　(深圳市红十字会医院药剂科　深圳518029)

　　摘要　目的:探索有效的抗癫痫化学成分。方法:用色谱和光谱分析法分离和鉴定。结果:从月腺大戟根甲醇提取液的沉淀部分,鉴定了2个化合物,分别为二十九烷醇210和242亚甲基环阿尔廷醇。结论:均为首次从该植物中分离得到。

关键词　月腺大戟　廿九烷醇210　242亚甲基环阿尔廷醇

　　中药狼毒为大戟科植物月腺大戟Euphor2 bia ebracteolata Hayata及狼毒大戟 E.f ischeri2 ana Steud.的干燥根。临床多用于癌症和结核病的治疗[1,2]。近年来我们曾对月腺大戟的水煎液及碱性提取液进行了动物的抗惊厥实验[3,4],并试用于癫痫病人的治疗,结果显示有明显的抗癫痫作用[5]。关于月腺大戟的化学成分的研究,文献报道已分得有抗癌活性的二萜和抗结核有效成分双分子呋喃醛醚等化合物[6]。我们从月腺大戟干燥根中分得2个化合物,分别鉴定为二十九烷醇210(102mona2 cosarnol)和242亚甲基环阿尔廷醇(242得到。另外还分得豆甾醇和胡萝卜甙。

1　仪器和药材

Boetius显微熔点测定仪(未校正),Perkin2 Elmer237红外光谱仪,Varian XL2300核磁共振仪(TMS内标),Finnigan1020OWA型GC/MS 仪。药材狼毒购自山西省药材公司,经山西医科大学中药教研室明东升鉴定为 E.ebracteola2 ta Hayata的干燥根。

2　提取分离

干燥月腺大戟根碎块2kg,甲醇回流提取3次(每次4h),合并提取液,放置过夜。过滤得淡黄色的沉淀物0.72g。沉淀物经硅胶低压柱

()Isolation and Identif ication of Tw o Flavonoids from Ta raxacum mongolicum H and.2Mazz.

Ling Yun,Bao Y anyan and Guo Xiufang

(Department of Pharmacy,Navy G eneral Hospital,Beijing100037)

Xu Y ang,Cai Shaoging and Zheng J unhua

(College of Pharmacy,Beijing Medical University,Beijing100083)

Abstract　Objective:To study the chemical constituents of Taraxacum mongolicum.Method:Compounds were sep2 arated by column chromatography on silica gel and polyamide,and thier structures were determined by spectral analysis and chemical evidence.R esult:Two flavonoid compounds were separated and elucidated as isoquercitrin and hyperin.Conclu2 sion:These two compounds were isolated from the plant for the first time.

K ey w ords　Taraxacum mongolicum;flavonoids

(original article on page225)

Studies on Chemical Constituents of Euphorbia ebracteolata Ilayata

Sun Xiaofei(Department of Pharmaceutical Science,Shanxi Medical University,Taiyuan030001)

Wang Shuping(Shanxi Oncological Hospital,Taiyuan030013)

Abstract　Objective:To search for the effective anti2epilepsiy components from the Chinese folk drug Langdu,the root of Euphorbia ebracteolata.Method:Chromatography and spectroscopic analysis were used to isolate and elucidate the chemical constituents in the plant.R esult:Four compounds,namely102nonacosanol,242methylenecycloartanol,stigmasterol and dacosterol have been isolated from the precipitate of the plant’s methanol extract.Conclusion:102nonacosarnol and242 methylenecycloartanol were obtained from the root of E.ebracteolate for the first time.

K ey w ords　Euphorbia ebracteolata;102nonacosarnol;242methylenecycloartanol;stigmasterol;dacosterol

(original article on page226)

Influence of Functional G roups of H uatanyuxin

Decoction on C a2+T ransmembrane Influx in R at Aorta

Mo Shangwu,Liu Ning and Jin Jiannan

(Institute of Nuclear Science and Technology,Sichuan Union Univeristy,Chengdu6100)

Ding Weihuang,Ruan Xiaoyan and Qing Huaile

(Sichuan Institute of Traditional Chinese Medicine,Chengdu610041)

Abstract　Objective:To study the Ca2+antagonistic effect of functional groups of Huatanyuxin decoction.Method: The　45Ca transmembrane influx technique was used to measure the Ca2+blocking effect of leak,receptor2operated Ca2+ channel(ROC)and potential2dependent Ca2+channel(PDC)in rat aorta.R esult:ROC and PDC could be blocked when the complex prescription was used at concentrations of0.5～5mg/ml.Among the functional groups,Huoxue group(acti2 vating blood)and Xinqi group(promoting and normalizing flow of vital energy)showed better Ca2+antagonistic effect. Conclusion:The mechanism of therapeutic effect of Huatanyuxin decoction may be related to its Ca2+blocking effect simi2 lar to verapamil.

K ey w ords　complex prescription;calcium antagonist;radionuclide　45Ca

(original article on page232)

Cerebral Protective E ffects of Some Compounds Isolated from T raditional Chinese H erbs

Ma Liyan,Xiao Peigen and Guo Baolin

(Institute of Medicinal Plants,Chinese Academy of Medical Sciences and Peking Union Medical College,Beijing100094)

Wu J unhua,Liang Faquan and Dong Sijian

()