火绒草正丁醇层的化学成分研究
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摘要
火绒草[Leontopodium leontopodioides (Wild.) Beauv.],为菊科火绒草属植物。火绒草属在全世界共有56种,我国有40余种,主要集中在西南部和西部,其中有25种在民间作为药用植物。
本文作者对体积分数为60%的火绒草乙醇提取物正丁醇层的化学成分进行研究。采用反复硅胶柱色谱法、Sephadex LH-20柱色谱法、ODS柱色谱法和反复重结晶等方法进行分离纯化,得到了20个化合物,根据相关的理化性质和波谱学数据,鉴定了其中16个化合物的结构,分别为：1-{3-(β-D-glucopyranosyloxy)-2,3-dihydro-2-[1-(hydroxyl-methyl)vinyl]-1-benzofuan-5-y1}-ethanone (1),芹菜素-7-O-β-D-葡萄糖苷(apigenin-7-O-β-D-glucoside,2),6-羟基芹菜素-7-O-β-D-葡萄糖苷(6-hydroxyapigenin-7-O-β-D-glucoside,3),木犀草素-4'-O-β-D-葡萄糖苷(luteolin-4'-O-β-D-glucoside,4),木犀草素-3'-O-β-D-葡萄糖苷(luteolin-3'-O-β-D-glucoside,5),6-羟基木犀草素-7-O-β-D-葡萄糖苷(6-hydroxyluteolin-7-O-β-D-glucoside,6),槲皮素-3-O-β-D-葡萄糖苷(quercetin-3-O-β-D-glucoside,7),山柰酚-3-O-β-D-葡萄糖苷(kaempferol-3-O-β-D-glucoside,8),金圣草素-4'-O-β-D-葡萄糖苷(chrysoeriol-4'-O-β-D-glucoside,9),甘草苷(liquiritin,10),腺苷(adenosine,11),小檗碱(berberin,12),香草酸(vanillic acid,13),反式桂皮酸(trans-cinnamic acid,14),β-谷甾醇(β-sitosterol,15),胡萝卜苷(daucosterol,16)。其中,化合物3,7,8,9,10,11均为首次从火绒草属植物中分离得到,化合物1,4,5,6为首次从本植物火绒草中分离得到。
Leontopodium leontopodioides (Wild.) Beauv., is a plant from Leontopodium genus, Compositae.. There are 56 species in Leontopodium genus all over the world, and about 40 species in china. Leontopodium genus usually distribute in the southwest and west regions in our country. Among them,25 species are used as medicine.
The author has investigated the chemical constituents about the n-BuOH soluble fraction of the 60% EtOH extract from Leontopodium leontopodioides (Wild.) Beauv. Twenty compounds were isolated and repeatedly purified by multiple chromatographical techniques. Sixteen compounds were elucidated on the basis of physicochemical properties and spectra methods. They were 1-{3-(β-D-glucopyranosyloxy)-2,3-dihydro-2-[1-(hydroxymethyl)vinyl]-1-benzofuan-5-y1}-ethanone(1), apigenin-7-O-β-D-glucoside(2),6-hydroxyapigenin-7-O-β-D-glucoside(3), luteolin-4'-O-β-D-glucoside(4), luteolin-3'-O-β-D-glucoside(5), 6-hydroxyluteolin-7-O-β-D-glucoside(6), quercetin-3-O-β-D-glucoside(7), kaempferol-3-O-β-D-glucoside(8),chrysoeriol-4'-O-β-D-glucoside(9), liquiritin(10), adenosine(11), berberin(12), vanillic acid(13), trans-cinnamic acid(14),β-sitosterol (15), daucosterol (16). Among them, Compounds 3,7,8,9,10,11 were isolated from this genus for the first time, Compounds 1,4, 5,6 were isolated from this herb for the first time.
本文作者对体积分数为60%的火绒草乙醇提取物正丁醇层的化学成分进行研究。采用反复硅胶柱色谱法、Sephadex LH-20柱色谱法、ODS柱色谱法和反复重结晶等方法进行分离纯化,得到了20个化合物,根据相关的理化性质和波谱学数据,鉴定了其中16个化合物的结构,分别为：1-{3-(β-D-glucopyranosyloxy)-2,3-dihydro-2-[1-(hydroxyl-methyl)vinyl]-1-benzofuan-5-y1}-ethanone (1),芹菜素-7-O-β-D-葡萄糖苷(apigenin-7-O-β-D-glucoside,2),6-羟基芹菜素-7-O-β-D-葡萄糖苷(6-hydroxyapigenin-7-O-β-D-glucoside,3),木犀草素-4'-O-β-D-葡萄糖苷(luteolin-4'-O-β-D-glucoside,4),木犀草素-3'-O-β-D-葡萄糖苷(luteolin-3'-O-β-D-glucoside,5),6-羟基木犀草素-7-O-β-D-葡萄糖苷(6-hydroxyluteolin-7-O-β-D-glucoside,6),槲皮素-3-O-β-D-葡萄糖苷(quercetin-3-O-β-D-glucoside,7),山柰酚-3-O-β-D-葡萄糖苷(kaempferol-3-O-β-D-glucoside,8),金圣草素-4'-O-β-D-葡萄糖苷(chrysoeriol-4'-O-β-D-glucoside,9),甘草苷(liquiritin,10),腺苷(adenosine,11),小檗碱(berberin,12),香草酸(vanillic acid,13),反式桂皮酸(trans-cinnamic acid,14),β-谷甾醇(β-sitosterol,15),胡萝卜苷(daucosterol,16)。其中,化合物3,7,8,9,10,11均为首次从火绒草属植物中分离得到,化合物1,4,5,6为首次从本植物火绒草中分离得到。
Leontopodium leontopodioides (Wild.) Beauv., is a plant from Leontopodium genus, Compositae.. There are 56 species in Leontopodium genus all over the world, and about 40 species in china. Leontopodium genus usually distribute in the southwest and west regions in our country. Among them,25 species are used as medicine.
The author has investigated the chemical constituents about the n-BuOH soluble fraction of the 60% EtOH extract from Leontopodium leontopodioides (Wild.) Beauv. Twenty compounds were isolated and repeatedly purified by multiple chromatographical techniques. Sixteen compounds were elucidated on the basis of physicochemical properties and spectra methods. They were 1-{3-(β-D-glucopyranosyloxy)-2,3-dihydro-2-[1-(hydroxymethyl)vinyl]-1-benzofuan-5-y1}-ethanone(1), apigenin-7-O-β-D-glucoside(2),6-hydroxyapigenin-7-O-β-D-glucoside(3), luteolin-4'-O-β-D-glucoside(4), luteolin-3'-O-β-D-glucoside(5), 6-hydroxyluteolin-7-O-β-D-glucoside(6), quercetin-3-O-β-D-glucoside(7), kaempferol-3-O-β-D-glucoside(8),chrysoeriol-4'-O-β-D-glucoside(9), liquiritin(10), adenosine(11), berberin(12), vanillic acid(13), trans-cinnamic acid(14),β-sitosterol (15), daucosterol (16). Among them, Compounds 3,7,8,9,10,11 were isolated from this genus for the first time, Compounds 1,4, 5,6 were isolated from this herb for the first time.
引文
[1]温彩红,陈其秀,陈冉,等.火绒草的研究进展[J].内蒙古医学院学报,2005,27(5)：90-91.
[2]武彦文,高文远,苏艳芳,等.火绒草属植物的化学成分和药理活性研究进展[J].中国中药杂志,2005,30(4)：245-248.
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[5]张所命,李榕,林国强.藏药香芸火绒草Leontopodium haplophylloides化学成分的研究[J].有机化学,1998,18：259-262.
[6]安承熙,罗湘宁,杨绪启,等.香芸火绒草精油化学成分研究[J].分析测试技术与仪器,1995,1(4)： 40-47.
[7]高飞,周丽,陈琳,等.青藏高原植物香芸火绒草挥发油的超临界CO2萃取及GC-MS分析[J].草业与畜牧,2007(6)：1-3.
[8]姚建,张少贞.亚高山地区香芸火绒草挥发油的研究[J].西北植物学报,1997,17(6)：41-44.
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[14]Comey N, Grey A I, Hook I, et al. Sesquiterpenes from Leontopodium alpinum. PhytochemiStry,1999,50：1057-1060.
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[18]赵全成,吕景田,徐东铭.老头草有效成分的研究[J].中药通报,1984,9(6)：31-32.
[19]Comey N, Hook I, Sheridan, et al. Isolation of(S)-(-)-2,3-hydro-2,6,dimethyl-4H-benzopyran-4-one from roots of Leontopodium alpinum[J]. J Nat Prod,1997,60:148-149.
[20]甘青梅.藏药“扎托巴”的粉末鉴别[J].中国民族民间医药杂志,1997,27,35-37.
[21]黄利权,伍义行.火绒草的抗炎活性研究一对二甲苯所致小鼠耳廓肿胀及毛细血管通透性的影响[J].中兽医学杂志,2004,(2)：10-12.
[22]伍义行,王建国,郭福存,等.火绒草抑菌作用试验研究[J].时珍国药,2000,11(4)：289-290.
[23]焦淑萍,张立明,陈彪,等.火绒草降血糖作用的初步研究[J].中草药,1997,28(11)：673-675.
[24]黄利权,伍义行.火绒草及火绒草属植物研究进展[J].中兽医医药杂志,2004,3：24-26.
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[27]赵全成,周丹,李春生,等.老头草化学成分的研究[J].中药通报,1988,13(2)：34-35.
[28]常桂荣.中药老头草乙醇剂治疗慢性肾炎45例[J].中西医结合杂志,1987,7(11)：669-670.
[29]《全国中草药汇编》编写组.全国中草药汇编(上册)[M].第二版.北京：人民卫生出版社,1996：144.
[30]Dobner M. J., Ellmerer E. P., Schwaiger S, et al. New lignan, benzofuran, and sesquiterpene derivatives from the roots of Leontopodium alpinum and L. leontopodioides[J]. Helvetica Chimica Acta, (2003),86(3):733-738.
[31]张健,孔令义.蒌蒿叶的黄酮类成分研究[J].中草药,2008,39(1)：23-26.
[32]Peng Z F, Strack D, Baumert A, et al. Antioxidant flavonoids from leaves of Polygonum hydropiper L [J]. Phytochemistry,2003,62 (2):219-228.
[33]张永红,汪涛,芦志刚,等.鼬瓣花化学成分研究[J].中国中药杂志,2002,27(3)：206-208.
[34]梁侨丽,丁林生.扁豆花化学成分研究[J].中国药科大学学报,1996,27(4)：205-207.
[35]王祝年,韩壮,崔海滨,等.裸花紫珠的化学成分[J].热带亚热带植物学报,2007,15(4)：359-362.
[36]Lu Y, Foo L. Y. Flavonoid and phenolic glycosides from Salvia officinalis[J]. Phytochemistry,2000, 55(3):263-267.
[37]陈雏,张浩,顾恒,等.中国沙棘果实中的黄酮苷类成分[J].华西药学杂志,2007,22(4)：367-370.
[38]黄开毅,张冬松,高慧媛,等.黄独的化学成分[J].沈阳药科大学学报,2007,24(3)：145-147.
[39]Lu Y, Sun Y, Foo L. Y, et al. Phenolic glycosides of forage legume Onobrychis viciifolia, Phytoche-mistry,2000,55 (1):67-75.
[40]王英华,白虹,窦德强,等.栽培甘草中黄酮类成分的研究[J].西北药学杂志,2004,19(6)：252-253.
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[2]武彦文,高文远,苏艳芳,等.火绒草属植物的化学成分和药理活性研究进展[J].中国中药杂志,2005,30(4)：245-248.
[3]中国科学院中国植物志编辑委员会编.中国植物志(第75卷)[M].北京：科学出版社,1979,136-138.
[4]Stuppner H, Ellemer E P, Ongania K-H, et al. Bisabolane derivatives from Leontopodium alpinum. Helvetica Chimica Acta,2002,85(9):2982-2989.
[5]张所命,李榕,林国强.藏药香芸火绒草Leontopodium haplophylloides化学成分的研究[J].有机化学,1998,18：259-262.
[6]安承熙,罗湘宁,杨绪启,等.香芸火绒草精油化学成分研究[J].分析测试技术与仪器,1995,1(4)： 40-47.
[7]高飞,周丽,陈琳,等.青藏高原植物香芸火绒草挥发油的超临界CO2萃取及GC-MS分析[J].草业与畜牧,2007(6)：1-3.
[8]姚建,张少贞.亚高山地区香芸火绒草挥发油的研究[J].西北植物学报,1997,17(6)：41-44.
[9]周劲松,韦梅琴.香芸火绒挥发性化学成分研究[J].西北植物学报,2002,22(6)：1482-1484.
[10]涂永勤,董晓萍,彭腾,等.华火绒草黄酮化合物的研究[J].重庆中草药研究,2005,2：10-11.
[11]Tira S, Gaaleffi C, Modica GD. Flavonoids of gnaphaninea:Leontopodium alpinum[J]. Experentia, 1970,26:1192.
[12]Dashbalyn T S, Glyzin V T. Flavonoid glycosides from edelweiss Leontopdium Ochroleucum[J]. Chemistry of Natural Compounds,1978,14(6):690.
[13]Bicchi C, Frattini C, Nano GM, et al. Hesahydrofarnesylacetone from Phagnalon rupestre[J]. Relata Tech,1979,11 (9):64.
[14]Comey N, Grey A I, Hook I, et al. Sesquiterpenes from Leontopodium alpinum. PhytochemiStry,1999,50：1057-1060.
[15]Dobner MJ, Ellemer E P, Schwaiger S, et al. New lignan, benzofuran, and sesquiterpene derivatives from the roots of Leontopodium alpinum and L. leontopodioides. Helvetica Chimica Acta, 2003,86:733-738.
[16]赵全成,吕景田,徐东铭.老头草化学成分的研究[J].中草药,1984,15(3)：7-8.
[17]Paternestre M P, Passananti S, P.Venturella, et al. Alkanes and sterols from some Sideritis, Stachys,Leontopodium espelctia and Cistus Species.[J].Atti Accad Sci Lett Arti Palerm Part1,1971-1973,32-39.
[18]赵全成,吕景田,徐东铭.老头草有效成分的研究[J].中药通报,1984,9(6)：31-32.
[19]Comey N, Hook I, Sheridan, et al. Isolation of(S)-(-)-2,3-hydro-2,6,dimethyl-4H-benzopyran-4-one from roots of Leontopodium alpinum[J]. J Nat Prod,1997,60:148-149.
[20]甘青梅.藏药“扎托巴”的粉末鉴别[J].中国民族民间医药杂志,1997,27,35-37.
[21]黄利权,伍义行.火绒草的抗炎活性研究一对二甲苯所致小鼠耳廓肿胀及毛细血管通透性的影响[J].中兽医学杂志,2004,(2)：10-12.
[22]伍义行,王建国,郭福存,等.火绒草抑菌作用试验研究[J].时珍国药,2000,11(4)：289-290.
[23]焦淑萍,张立明,陈彪,等.火绒草降血糖作用的初步研究[J].中草药,1997,28(11)：673-675.
[24]黄利权,伍义行.火绒草及火绒草属植物研究进展[J].中兽医医药杂志,2004,3：24-26.
[25]江苏新医学院.中药大辞典[M].上海：上海科学技术出版社,1977：1688.
[26]沈阳部队后勤部卫生部编.东北常用中草药[J].沈阳辽宁出版社,1970：280.
[27]赵全成,周丹,李春生,等.老头草化学成分的研究[J].中药通报,1988,13(2)：34-35.
[28]常桂荣.中药老头草乙醇剂治疗慢性肾炎45例[J].中西医结合杂志,1987,7(11)：669-670.
[29]《全国中草药汇编》编写组.全国中草药汇编(上册)[M].第二版.北京：人民卫生出版社,1996：144.
[30]Dobner M. J., Ellmerer E. P., Schwaiger S, et al. New lignan, benzofuran, and sesquiterpene derivatives from the roots of Leontopodium alpinum and L. leontopodioides[J]. Helvetica Chimica Acta, (2003),86(3):733-738.
[31]张健,孔令义.蒌蒿叶的黄酮类成分研究[J].中草药,2008,39(1)：23-26.
[32]Peng Z F, Strack D, Baumert A, et al. Antioxidant flavonoids from leaves of Polygonum hydropiper L [J]. Phytochemistry,2003,62 (2):219-228.
[33]张永红,汪涛,芦志刚,等.鼬瓣花化学成分研究[J].中国中药杂志,2002,27(3)：206-208.
[34]梁侨丽,丁林生.扁豆花化学成分研究[J].中国药科大学学报,1996,27(4)：205-207.
[35]王祝年,韩壮,崔海滨,等.裸花紫珠的化学成分[J].热带亚热带植物学报,2007,15(4)：359-362.
[36]Lu Y, Foo L. Y. Flavonoid and phenolic glycosides from Salvia officinalis[J]. Phytochemistry,2000, 55(3):263-267.
[37]陈雏,张浩,顾恒,等.中国沙棘果实中的黄酮苷类成分[J].华西药学杂志,2007,22(4)：367-370.
[38]黄开毅,张冬松,高慧媛,等.黄独的化学成分[J].沈阳药科大学学报,2007,24(3)：145-147.
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