摘要
本论文研究了米口袋属植物米口袋,翠雀属植物大花翠雀的化学成分。采用常规的柱层析(CC)、短柱减压层析、重结晶等手段对其中的化学成分进行了分离,并利用IR、EI-MS、GC-MS、~1HNMR、~(13)CNMR、DEPT、~1H-~1H COSY、gHMQC、gHMBC等现代波谱技术,结合适当的化学方法确定了大部分化合物的结构。我们从米口袋(Gueldenstaedita multiflora Bge.)全草及根的水溶性部分氯仿提取物中得到一个化合物loliolidc(A_1),从非水溶性部分氯仿提取物中得到6个化合物,分别是:烈香杜鹃素Ⅰ(B_1),木栓醇(B_2),木栓醛(B_3),豆甾烷-4-烯-3-酮(B_4),A'-Neogammacer-22(29)-en-3β-ol,acetate(B_5),β-谷甾醇(B_6),其中化合物A_1、B_1、B_2、B_3、B_4、B_5为首次从该植物中分离得到,并且对米口袋中的挥发油成分进行了分析鉴定,主要成分为烷,烯,醇,酯,醛,酮等化合物,还含有少量萜类化合物。截止目前,米口袋的水溶性成分及挥发油成分研究未见报道。从大花翠雀(Delphinium grandiflorum L.)全草及根的氯仿部位中我们分离了16个化合物,鉴定了13个化合物的结构和一个化合物的类型,分别是大花翠雀素Ⅲ(Y_1),1-O-去甲基塔拉萨敏(Y_2),14-O-甲基-1-O-去甲基塔拉萨敏(Y_3),4',7-二甲氧基-5-羟基黄酮(Y_4),氨茴酰牛扁碱(Y_5),去氧牛扁碱(Y_6),草地乌头碱(Y_7),N-cirmamoyl-2-phenylethylamine(Y_8),甲基牛扁亭(Y_9),翠雀胺(Y_(10)),翠雀固灵(Y_(11)),大花翠雀素(Y_(12)),牛扁碱(Y_(13))和一个酰胺类生物碱(Y_(14))。其中生物碱大花翠雀素Ⅲ为未见文献报道过的新化合物,Y_2、Y_3、Y_4、Y_5、Y_6、Y_7、Y_8为首次从该植物中分离得到,并且首次从该植物中分离得到黄酮类化合物及酰胺类生物碱。
另外,论文第一章对地丁的分类,化学成分和药理活性的研究概况进行了综述。
In this M.D thesis,chemical constituents of Gueldenstaedita multiflora Bge.、Delphinium grandiflorum L.had been studied.The compounds were isolated by means of silica gel column chromatography(CC),short column chromatography by reduce pressure and recrystallization et al.The structures of these compounds were determined by chemical transformations and spectroscopic identification including IR、EI-MS、GC-MS、~1HNMR、~(13)CNMR、DEPT、~1H-~1H COSY、gHMQC、gHMBC. From the Gueldenstaedita multiflora Bge.,the identified seven compounds were: loliolide(A_1),LiexiangdujuanineⅠ(B_1),Friedelinol(B_2),Friedelin(B_3), Stigmast-4-en-3-one(B_4),A'-Neogammacer-22(29)-en-3β-ol,acetate(B_5),β-sitosterol(B_6),Compounds A_1,B_1~B_6 were obtained from this plant for the frist time and compound A_1 was water-solubility,the others were nonwater-solubility。From the Delphinium grandiflorum L.,the identifyied thirteen compounds were: grandiflorineⅢ(Y_1),isotalatizidine(Y_2),14-O-methylisotalatizidine(Y_3), 4',7-dimethoxy-5-hydroxyflavone(Y4),anthranoyllycoctonin(Y_5),deoxylycoctonine (Y_6),umbrosine(Y_7),N-cinnamoyl-2-phenylethylamine(Y_8),methyllycaconitine (Y_9),delcosine(Y_(10)),delsoline(Y_(11)),grandiflorine(Y_(12)),lycoctonin(Y_(13)) and a amide alkaloid(Y_(14)).Above all of them,compound grandiflorineⅢ(Y_1)was a new diterpene alkaloid,and compounds Y_2~Y_8 were obtained from this plant for the frist time.The part of soluble chemical constituents and its volatile oil constituents of Gueldenstaedita multiflora Bge.have not been reported previously.
Besides,The classification,chemical constituents and pharmacological activities of Diding were summarized in the first part.
引文
[1]高锦明,廖蓉苏,高黎明等.植物化学.北京:科学出版社,2003.
[2]中国植物学会.中国植物学史.北京:科学出版社,1994.
[3]陈丽,王军宪,栗燕,常永红.米口袋属植物研究概况.陕西中医,2001,22(3):184-185
[4]吴银生.地丁的本草考证.苏州医学,1987,(3):31
[5]崔树德主编.中药大全.哈尔滨:黑龙江科技出版社,1989:289
[6]江苏新医学院编.中药大词典,上册.上海:上海人民出版社,1977:800
[7]徐维芬,霍德兰,赵华英.地丁药材凝胶电泳层析法的真伪鉴别.山东中医杂志,1988,17(4):178-179
[8]江苏新医学院编.中药大词典,上、下册.上海:上海科学技术出版社,1986:800
[9]刘寿山主编.中药研究文献摘要(1962-1974).北京:科学出版社,1979:290
[10]王旭红,秦民坚,余国奠.堇菜属药用植物研究概况与其资源利用前景.中国野生植物资源,2003,22(4):36-37
[11]刘湘新.紫花地丁的有效成分分析及抗菌作用研究.中兽医医药杂志,2004(3):16-18.
[12]梁雪芹.紫花地丁中微量元素浅析.黑龙江医药,1995,8(3):166-167.
[13]董乙文,胡玉涛.紫花地丁的研究概况.中国林副特产,2006,(82):78-80
[14]黄海.一种脂肪酶激活剂的性质的初步研究.上海大学学报(自然科学版),1999,5(3):249-251.
[15]董爱文.紫花地丁中维生素C提取及稳定性研究.食品科学与技术,2004(10):49-54.
[16]董爱文.紫花地丁在不同季节总黄酮含量的变化.中国医药工业志,2004,35(10):592-593.
[17]Bo Qin,etal.Separation and Quantitative Determination of Three Coumarinsin the Chinese Traditional Drug Zi hua Di ding,Herba Violae,by High Performance Liquid Chromatography.Journal of Chinese Pharmaceutical Sciences,1994,3(2):157-163.
[18]陈启洁.紫花地丁的开发利用与栽培技术研究.国土与自然资源,2004(1):95-96.
[19]暨南大学药学院,于荣敏,王春盛,宋丽艳.罂粟科植物的化学成分及药理作用研究进展.上海中医药杂志,2004,38(7):59-61
[20]CA,1988,108:109510r
[21]中药志第四册 1988,22
[22]曾伟光等.苦地丁生物碱的薄层光密度测定药物分析杂志,1987,7(6):323
[23]朱蓉,朱大元,徐任生.地丁化学成分的研究.中草药,1984,15(8):1-3
[24]王军宪,朱蓉.米口袋化学成分的研究.西北植物学报,1989,9(2):127-130
[25]周凤梧主编.中药学.济南:山东科技出版社,1986:185
[26]张贵君,徐国钧主编.常用中药鉴定大全.哈尔滨:黑龙江科学技术出版社,1993:297
[27]杨维霞,周乐,耿会玲,秦宝福.龙胆科药用植物化学成分的研究现状.西北植物学报2003,23(12):2235-2240
[28]江苏省植物研究所.新华本草纲要[M].上海:上海科技出版社,1991:387..
[29]孔增科.实用中药手册[M].天津:天津出版社,1996:83.
[30]王国英,黄翠轩,蒋家雄.Pathology observation of experimental protect function by Gentiopicroside to big rat liver cell[J].云南医药,1993,14(4):242
[31]MAWG,NICOLAFUZZATI,JEAN-LUCWOLFENDER,etal.Further acylated secoiridoid glucosides from Gentiana rhodantha[J].Phytochemistry,1996,43(4):805-810.
[32]杨肖锋,宋纯清.Study of gentiopicroside metabolization of fungus community in intestines[J],中国中药杂志,2000,25(11):673-675
[33]谭沛,刘永隆.Components of xanthonesin plant[J].Research and Exploit Natural Product(天然产物研究与开发),995,7(1):45-54
[34]傅永丰,孙南君 The study of chemical components of Gentiana macrophylla[J].Learned Journal of Medicine(药学学报),1958,6(4):198-203.
[35]郭亚建,陆蕴如.The study of turning Gentiopicroside in to Gentiana[J].Medicine Analysis(药物分析杂志),1983,3(5):268-271
[36]许秀芝,田轩.Study of chemical components of Gentiana tizuensis[J].Chinese Traditional and Herbal Drugs(中草药),2000,25(4):225-226.
[37]MINBS,KIMYHLEESM.Cytotoxic triterpenes from crataegus pinnatifida[J].Archives of Pharmacal Research,2001,23(2):155-158.
[38]郭信芳,陈昌彪.Isolation and identification of gentianine from Swertiadavidi[J].Chinese Traditional and Herbal Drags(中草药),1980,11(5):200
[39]MIURAN.Mataumotoy Proiective effects of triterpene compound sagainst the cytotoxicity of cadmium in HepG2 cells[J].Molecular Pharmacology,1999,56(6):1324-1328.
[40]EDETM.ANAM.Two triterpenoids from Gentiana neurotheca[J].Phytochemistry,1998,48(1):211-213.
[41]KUOSHIN-HSIEN,YENMING-HONG,CHUNGMEI-ING,LIN,CHUN-NAN.A flavone C-glycoside and an aromatic glucose de from Gentiana species[J].Phytochemistry, 1996,41(1):309.
[42]LINCHUN-NAN,SHIH-HSIEN,CHUNGMEI-ING,KOFENG-NIEN,TENGCHE-MING.A new flavone C-glycoside and antiplatelet and vasorelaxing flavones from Gentiana arisanensis[J].Nat.Prod.,1997,60(8):851-853.
[43]赵红,顾定伟,张淑杰,梅双双.紫花地丁水煎剂调节小鼠免疫细胞功能的体外研究.福建中医学院学报,2003,13(2):27-30
[44]刘湘新,刘进辉,刘自逵,周可炎,谭超.紫花地丁的有效成分分析及抗菌作用研究.中兽医医药杂志.2004,(3):16-18
[45]中华人民共和国卫生部药典委员会.中国药典一部.化学工业出版社,2000:278.
[46]梁俨.犁头草治疗化脓性感染.江西医药,1966,(7):372
[47]青岛研究小组.中草药苦地丁的研究.中草药通讯,1972,(5):16-19
[48]潘溪庆等.苦地丁生物碱的研究.药学通报,1981,4:57
[49]吕惠子,崔兴日,王广录.苦地丁的化学成分与药理.中国野生植物资源2002,21(4):54-55
[50]杨敬格等.赣南医学院学报,1991,11(4):198
[51]程必勇·地丁、紫花地丁本草考.陕西中医学院学报,1988,11(2):33-35
[52]郭爱华.龙胆科獐牙菜属药用植物化学成分和药理作用的研究进展.山西中医学院学报,2005,6(1):57-59
[53]王廷慧,赵润芝,陈兵,白龙.苦地丁抗炎、镇痛作用的实验研究.延安大学学报(自然科学版),1997,16(4):81-84
[54]魏陈.紫花地丁的园林栽培.黑龙江林业,2001,(5):23.
[55]陈启洁,吴姝菊,李君霞,赵宁.紫花地丁的开发利用与栽培技术研究.国土与自然资源研究,2004,(1):95-96
[56]《中华人民共和国药典》95年版一部附录:20
[57]吕惠子,崔兴日,王广录.苦地丁的化学成分与药理.中国野生植物资源,2002,21(4):54-55
[58]Yu Rongmin,Wang Ying,Ma Li,etal.Production of active alkaloids by elicited Papaver nudicaule cell suspension cultures[J].Pharmaceutical Biotechnology,2003,10(4):218-222.
[59]王莹,马莉,于荣敏等.野罂粟悬浮细胞培养及其野罂粟生物碱的产生[J].药物生物技术,2003,10(2):72-76.
[60]程红霞,于荣敏,张辉等.野罂粟试管苗培养及其愈伤组织诱导[J].沈阳药科大学学报, 2001,18(2):128-130.
[61]国家药典委员会编.中华人民共和国药典.2000版一部.北京:化学工业出版社,2000:附录28
[62]《全国中草药汇编》编写组编.全国中草药,下册.北京:人民卫生出版社,1975:806
[63]中国科学院植物研究所主编.中国高等植物图鉴.第二册.北京:科学出版社,1974:413-415
[64]《河北植物志》编写组编.河北植物志.第一卷.石家庄:河北科学技术出版社,1985:721-723
[65]李世全主编.秦岭巴山天然药物志.西安:陕西科学技术出版社,1987:601
[66]中国科学院兰州沙漠研究所编.中国沙漠植物志.第二卷.北京:科学出版社,1987:292
[67]中国科学院西藏研究所编.西藏植物志.第二卷.北京:科学出版社,1985:793.796
[68]中国科学院昆明植物研究所编.云南种子植物名录.上册.昆明:云南人民出版社,1084:603-604
[69]TAN REN-XIANG,KONG LING-DONG.Secoirdoids from Gentiana siphonantha[J].Phytochemistry,1997,46(6):1035-1038.
[70]HOSTETTMANNK,WABGERH.Components of Xanthone[J].Phytochemistry,1977,(16):821.
[71]KEIZO HOSOKAWA,ERIFUKUSHI,JUNKAWABATA,CHIHARUFUJII,etal.Three acylated cyaniding glucosides in pink flowers Of Gentiana[J].Phytochemistry,1997,40(3):941-944.
[72]KEIZO HOSOKAWA,ERIFUKUSHI,JUNKAWABATA,CHIHARUFUJII,etal.Seven acylated anthocyanins in blue flowers of Gentiana[J].Phytochemistry,1997,45(1):167-171.
[73]RODRIGUEZ-S,WOLFENDER-J.L,HAKIZAMUNGU-E,HOSTETTMANN-K.An antifungal naphthoquinone,xanthones and secoiridoids from Swertiac alycina[J].PlantaMedica,1995,61(4):362-364.
[74]中国科学院西北植物研究所编著.秦岭植物志,第一卷(第三册):种子植物.北京:科学出版社,1981,49
[1]陈丽,王军宪,栗燕,常永红.米口袋属植物研究概况.陕西中医,2001,22(3):184-185
[2]中国科学院西北植物研究所编著。秦岭植物志,第一卷(第三册):种子植物。北京:科学出版社,1981,49
[3]朱蓉,朱大元,徐任生.地丁化学成分的研究.中草药,1984,15(8):1-3
[4]王军宪,朱蓉.米口袋化学成分的研究.西北植物学报,1989,9(2):127-130
[5]Naomasa Okada,Katsutoshi Shirata,Mitsuru Niwano,etal.Immuno suppressive activity of amonoterpene from Eucommia Ulmoides[J].Phytochemistry,1994,37(1):281.
[6]Zheng shang-zhen,Ma xue-mei,Que sheng,Yang hong-peng,Shen xu-wei.Chemical constituents of Rhododendron Anthopogonoides Maxim.Natural product research and development,2003,15(5):387-389
[7]Li KangHo,Chiann RongChang,Yuan ShiunChang.Chemical components from Triumfettabartramia[J].J.Chin Chem.Soc,1995,42(1):93-95.
[8]A kihisa T,Y amamoto K,T amura T,etal.Triterpenoid Ketones from Lingnaniachungii Mcclure:Arborinone,Friedelinand Glutinone[J].Chem.Pharm.Bull,1992,40(3):789-791.
[9]潘宣,程东亮,何兰.白山菊化学成分的研究[J].中草药,1996,27(1):55-56.
[10]Hirota H,Moriyama Y,Tsuyuki T,etal.The High Resolution Mass of Spectraof Shionane and Friedelane Derivatives[J].Bull Chem.Soc Jpn,1975,48(6):1884-1888.
[11]胡昌奇,王林,姚辉农.杏香兔耳风的化学成分的研究[J].中草药,1983,14(11):486-488.
[12]蒋毅,李鹤罗.南蛇藤活性成分的研究[J].中草药,1996,27(2):73-74.
[13]刘安等.乌藤化学成分的研究.中草药,2002,3(33):205-206
[14]赵奎君,刘锁兰,杨隽,李秀清.大狼毒化学成分的研究.中国中药杂志,1995,20(3):169-171
[15]The sadter stundane speetra 164DIK.
[16]Wright T L.Can.J.Chem,1978,56:1898.
[1].节香挥发油的气相色谱-质谱联用分析。
[2]朱蓉,朱大元,徐任生.地丁化学成分的研究.中草药,1984,15(8):1-3
[3]王军宪,朱蓉.米口袋化学成分的研究.西北植物学报,1989,9(2):127-130
[4]Massada Y.Analysis of Essential Oils by Gas Chromatography and Mass Spetrometry.New York:Jone and Sons.Inc.1976,36
[5]Heller S R,Milne G W A.EPA/NIH Mass Spetral data base.Washington,US:Government Printing Office,1978,67
[6]李祖光,李新华,刘文涵等。节香鲜花香气化学成分的研究。林产化学与工业,2004,24(1):83-86
[1]王锋鹏.乌头属和翠雀属植物中生物碱化学研究概况[J].药学学报,1981,16(12):943-959
[2]杨崇仁,郝小江,陈泗英.毛茛科植物中的二萜生物碱[J].云南植物研究,1979,(2):1-48
[3]丁立生,陈维新.天然C_(19)-二萜生物碱的核磁共振谱(Ⅰ)[J].天然产物研究与开发,1989,1:6-32
[4]王建莉,周先礼,王锋鹏.秦岭翠雀花中生物碱成分的研究[J].天然产物研究与开发,2003,15(6):498-502
[5]李从军,陈迪华.大花雀翠地上部分的生物碱[J].植物学报,1993,35(1):80-83
[6]李从军,陈迪华.大花雀翠的新二萜生物碱[J].植物学报,1992,34(6):466-469
[7]Nyamdari Batbayaia,Shiiter Enkhzayaa,Jigjidsuren Tunsaga,Dulamjav,Batsurena,David S.Rycroft b,Susanne Sprollc,Franz Bracher.Norditerpenoid alkaloids from Delphinium species.Phytochemistry,2003,62:543-550
[8]Pelletier S.W.,Mody N.V.and Katsui N..The structures of sachaconitine and isodelphinine from Aconitm miyabei Nakai[J].Tetrahedron letters,1977,(46):4027-4030
[9]Sirotenko E.G.,Rashkes Ya.V.and Usmanova S.K..mASS Spectrometry of diterpene alkaloids in plants of the genus Aconitum.Khim.Prir.Soedin.,1989,538
[10]Bandoni,A.L.,Medina,J.E.,Rondina,R.V.D.,Coussio,.I.D..Genus Baccharis L.I:Phytochemical analysis of a non polar fraction from B.Crispa SprengeI[J].PlantaMed,1978,34(3):328-331
[11]Shamma M,Chinnesamy P and Miana GA.The alkaloids of Delphinium cashmifianum..J.Nat.Prod.,1979,42:615
[12]A.J.Jones and M.H.Benn.Diterpenoid alkaloids from Delphinium species.Canad.J.Chem,1973,51(4):486-499
[13]V.A.Tel'nov,N.M.Golubev and M.S.Yunusov.A new alkaloid from Aconitum umbrosum.Khim.Prirod.Soedinenii,1976,(5):675-676
[14]V.I.Akhmedzhanova and D.Batsuren.Alkaloids and Flavonoids of Oxytropis muricata.Chemistry of Natural Compounds,1997,33(3):326-328.
[15]Samir A.Ross,Mounirah A.Al-Azeib,Kesanapalli S.Krishnaveni,Frand R.Frouczek and Charles L.Burandt.Alkamides from the Leaves of Zanthoxylum syncarpum.J.Nat.Prod.,2005,68:1297-1299
[16]Deng Y P.diterpenoid alkaloids from roots of Delphinium grandiflorum L.[J].Fitoterapia,1993,64(3):282.
[17]Pelletier SW,Mody NV and Varughase KI.Structure revision of 37 octonine-related diterpenoid alkaloids.J Am Chem Soc,1981,103:6536
[18]H.Takayama,Y.Hitotsuyanagi,K.Yamaguchi,N.Aimi and S.I.Sakai.Chem.Pharm.Bull.,1989,37,548
[1]Skehan P,Storeng R,Scudiero D.Newcolorimetric cytotoxicity assay for anticancer drug screening.Journal of National Cancer Institute,1990,82:1107-1112.