细梗香草化学成分的分离鉴定
|
摘要
目的:对细梗香草正丁醇部位进行系统的化学成分研究。方法:取细梗香草药材粉碎,用70%乙醇回流提取,减压回收溶剂得浸膏,浸膏经水溶解后,用正丁醇萃取,得到正丁醇部位,采用大孔树脂柱,中压ODS柱色谱,硅胶柱色谱,LH-20型羟丙基葡聚糖凝胶(Sephadex LH-20)柱色谱和制备高效液相色谱等技术手段进行分离纯化,分离得到单体化合物,并经波谱数据分析和文献数据鉴定化合物的结构。结果:从细梗香草正丁醇提取物中分离得到15个化合物,其中6个皂苷类和9个黄酮苷类化合物,分别鉴定为细梗香草皂苷B(1),细梗香草皂苷C(2),kaempferol-3-O-β-D-xylopyranosyl(1→3)-[4-O-E-pcoumaroyl-α-L-rhamnopyranosyl (1→2)][β-D-glucopyranosyl (1→6)]-β-D-galactopyranoside-7-O-α-L-rhamnopyranoside (3),kaempferol-3-O-{[β-D-xylopyranosyl (1→3)-α-L-rhamnopyranosyl (1→6)][α-L-rhamnopyranosyl (1→2)]}-β-D-3-trans-pcoumaroylgalactopyranoside(4),细梗香草皂苷K(5),3β-O-{α-L-rhamnopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→4)-[O-β-Dglucopyranosyl-(1→2)]-α-L-arabinopyranosyl}-16α-hydroxyolean-28,13β-olide (6),细梗香草皂苷I(7),quercetin-3-O-(2″,6″-diO-α-rhamnopyranosyl)-β-galactopyranoside(8),kaempferol-3-O-{[β-D-xylopyranosyl (1→3)-α-L-rhamnopyranosyl (1→6)][α-Lrhamnopyranosyl-(1→2)]}-β-D-galactopyranoside (9), kaempferol-3-O-[2-glucopyranosyl (1→3) rhamnopyranosyl-6-rhamnopyranosyl]-β-D-galactopyranoside (10),kaempferol-3-O-α-L-rhamnopyranosy-(1→2)-[α-L-rhamnopyranosy-(1→6)]-β-Dgalactopyranoside (11),capilliposide I (12),kaempferol-3-O-{(β-D-glucopyranosyl-(1→3)-[4-O-(E-p-coumaroyl)]-α-Lrhamnopyranosyl-(1→6)-(β-D-galactopyranoside)}-7-O-α-L-rhamnopyranoside (13),kaempferol-3-O-{[β-D-glucopyranosyl (1→3)]-4-O-(E-p-coumaroyl)}-α-L-rhamnopyranosyl(1→6)-β-D-glucopyranoside-7-O(4-O-acetyl)-α-L-rhamnopyranoside (14),(3β,20S,23S,24R)-3,20,23,24,25,29-hexahydroxydammaran-21-oic acid-21,23-lactone 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside(15)。结论:化合物3,4,6,9,10,13～15为首次在该植物中分离得到。
Objective: To systemically study the chemical constituents of n-butanol fraction from Lysimachia capillipes. Method: The whole plant of L. capillipes was crushed into power, extracted by 70%methanol,concentrated under reduced pressure, and then its n-butanol extract was obtained by fractional extraction. The compounds from n-butanol fraction were isolated and purified by macroporous resin column chromatography,medium pressure ODS, silica gel, Sephadex LH-20 and preparative HPLC. Their structures were identified on the basis of spectral analysis and comparison with literature data. Result: Fifteen compounds including 6 saponins and 9 flavonoid glycosides were isolated from L. capillipes, and were identified as ascapilliposide B( 1) and capilliposide C( 2), kaempferol-3-O-β-D-xylopyranosyl( 1 → 3)-[4-O-E-pcoumaroyl-α-L-rhamnopyranosyl( 1 → 2) ] [β-D-glucopyranosyl( 1 → 6) ]-β-D-galactopyranoside-7-O-α-Lrhamnopyranoside( 3),kaempferol-3-O-{ [β-D-xylopyranosyl( 1→3)-α-L-rhamnopyranosyl( 1→6) ][α-Lrhamnopyranosyl( 1→2) ]}-β-D-3-trans-p-coumaroylgalactopyranoside( 4),capilliposide K( 5),3β-O-{ α-Lrhamnopyranosyl-( 1 → 2)-O-β-D-glucopyranosyl-( 1 → 4)-[O-β-D-glucopyranosyl-( 1 → 2) ]-α-Larabinopyranosyl) }-16α-hydroxyolean-28,13β-olide( 6),capilliposide I( 7),quercetin-3-O-( 2″,6″-di-O-α-rhamnopyranosyl)-β-galactopyranoside( 8), kaempferol-3-O-{ [β-D-xylopyranosyl( 1 → 3)-α-Lrhamnopyranosyl( 1→6) ] [α-L-rhamnopyranosyl-( 1 →2) ]}-β-D-galactopyranoside( 9),kaempferol-3-O-[2-glucopyranosyl( 1 →3) rhamnopyranosyl-6-rhamnopyranosyl]-β-D-galactopyranoside( 10),kaempferol-3-O-α-L-rhamnopyranosy-( 1→2)-[α-L-rhamnopyranosy-( 1→6) ]-β-D-galactopyranoside( 11),capilliposide I( 12),kaempferol-3-O-{( β-D-glucopyranosyl-( 1 →3)-[4-O-( E-p-coumaroyl) ]-α-L-rhamnopyranosyl-( 1→6)-( β-D-galactopyranoside) }-7-O-α-L-rhamnopyranoside( 13),kaempferol-3-O-{ [β-D-glucopyranosyl( 1→3) ]-4-O-( E-p-coumaroyl) }-α-L-rhamnopyranosyl( 1→6)-β-D-glucopyranoside-7-O( 4-O-acetyl)-α-L-rhamnopyranoside( 14),and( 3β,20 S,23 S,24 R)-3,20,23,24,25,29-hexahydroxydammaran-21-oic acid-21, 23-lactone 3-O-β-D-glucopyranosyl-( 1 → 6)-β-D-gluco-pyranoside( 15). Conclusion: The compounds 3,4,6,9,10,13-15 were isolated from this plant for the first time.
Objective: To systemically study the chemical constituents of n-butanol fraction from Lysimachia capillipes. Method: The whole plant of L. capillipes was crushed into power, extracted by 70%methanol,concentrated under reduced pressure, and then its n-butanol extract was obtained by fractional extraction. The compounds from n-butanol fraction were isolated and purified by macroporous resin column chromatography,medium pressure ODS, silica gel, Sephadex LH-20 and preparative HPLC. Their structures were identified on the basis of spectral analysis and comparison with literature data. Result: Fifteen compounds including 6 saponins and 9 flavonoid glycosides were isolated from L. capillipes, and were identified as ascapilliposide B( 1) and capilliposide C( 2), kaempferol-3-O-β-D-xylopyranosyl( 1 → 3)-[4-O-E-pcoumaroyl-α-L-rhamnopyranosyl( 1 → 2) ] [β-D-glucopyranosyl( 1 → 6) ]-β-D-galactopyranoside-7-O-α-Lrhamnopyranoside( 3),kaempferol-3-O-{ [β-D-xylopyranosyl( 1→3)-α-L-rhamnopyranosyl( 1→6) ][α-Lrhamnopyranosyl( 1→2) ]}-β-D-3-trans-p-coumaroylgalactopyranoside( 4),capilliposide K( 5),3β-O-{ α-Lrhamnopyranosyl-( 1 → 2)-O-β-D-glucopyranosyl-( 1 → 4)-[O-β-D-glucopyranosyl-( 1 → 2) ]-α-Larabinopyranosyl) }-16α-hydroxyolean-28,13β-olide( 6),capilliposide I( 7),quercetin-3-O-( 2″,6″-di-O-α-rhamnopyranosyl)-β-galactopyranoside( 8), kaempferol-3-O-{ [β-D-xylopyranosyl( 1 → 3)-α-Lrhamnopyranosyl( 1→6) ] [α-L-rhamnopyranosyl-( 1 →2) ]}-β-D-galactopyranoside( 9),kaempferol-3-O-[2-glucopyranosyl( 1 →3) rhamnopyranosyl-6-rhamnopyranosyl]-β-D-galactopyranoside( 10),kaempferol-3-O-α-L-rhamnopyranosy-( 1→2)-[α-L-rhamnopyranosy-( 1→6) ]-β-D-galactopyranoside( 11),capilliposide I( 12),kaempferol-3-O-{( β-D-glucopyranosyl-( 1 →3)-[4-O-( E-p-coumaroyl) ]-α-L-rhamnopyranosyl-( 1→6)-( β-D-galactopyranoside) }-7-O-α-L-rhamnopyranoside( 13),kaempferol-3-O-{ [β-D-glucopyranosyl( 1→3) ]-4-O-( E-p-coumaroyl) }-α-L-rhamnopyranosyl( 1→6)-β-D-glucopyranoside-7-O( 4-O-acetyl)-α-L-rhamnopyranoside( 14),and( 3β,20 S,23 S,24 R)-3,20,23,24,25,29-hexahydroxydammaran-21-oic acid-21, 23-lactone 3-O-β-D-glucopyranosyl-( 1 → 6)-β-D-gluco-pyranoside( 15). Conclusion: The compounds 3,4,6,9,10,13-15 were isolated from this plant for the first time.
引文
[1]江西省食品药品监督管理局.江西省中药材标准[M].上海:上海科学技术出版社,2014:337-339.
[2]中国科学院《中国植物志》编辑委员会.中国植物志[M].北京:科学出版社,1989.
[3]田景奎.珍珠菜属两种药用植物化学成分的研究[D].北京:北京协和医学院,2002.
[4]梁冰倩,胡正芳,戚进.湖北麦冬地下部分化学成分[J].中国实验方剂学杂志,2018,24(19):37-41.
[5]刘勇,张琪,陈勐,等.满山香生药学研究[J].时珍国医国药,2015,26(9):2178-2180.
[6]应弘梅,陈润泽,郭达伟,等.细梗香草中皂苷的含量测定及其抗肿瘤作用研究[C]//中国药学会. 2010年中国药学大会暨第十届中国药师周论文集:2010年卷,天津:出版社不详,2010:2672-2679.
[7]程忠哲.细梗香草两个主要抗肿瘤活性皂苷成分的药代动力学研究[D].武汉:华中科技大学,2015.
[8]费正华,陈云亮,马胜林.细梗香草总皂苷诱导肺癌细胞H460凋亡及其机制的研究[J].浙江医学,2014,36(9):742-746.
[9]于淼,冉小库,窦德强,等.孔雀草茎、叶化学成分的分离鉴定[J].中国实验方剂学杂志,2018,24(7):64-68.
[10] Mehdi C,Philippe C,Catherine V S,et al. Acylated flavonol pentaglycosides from Baphia nitida leaves[J].Phytochem Lett,2009,3(2):70-74.
[11] Nabil S,Bernard F,Katia G F,et al. New flavonol tetraglycosides from Astragalus caprinus[J]. Chem Pharm Bull,2002,50(7):981-984.
[12] LIANG B,ZHANG L,TIAN J K. Isolation and characterization of two new saponins from Lysimachia capillipes[J]. Carbohydr Res,2006,341(14):2444-2448.
[13] Bloor S J,LU Q. Cytotoxic saponins from New Zealand Myrsine species[J]. J Nat Prod,1994,57(10):1354-1360.
[14]田景奎,邹忠梅,徐丽珍,等.细梗香草中的两个新三萜皂苷[J].药学学报,2004,39(9):722-725.
[15] Yuko H,Tomoyuki F,Toshiyuki I,et al. Antioxidative properties and flavonoid composition of Chenopodium quinoa seeds cultivated in Japan[J]. Food Chem,2010,119(4):1300-1306.
[16] Semmar N,Fenet B,Gluchoff Fiasson K,et al. New flavonol tetraglycosides from Astragalus caprinus[J].Chem Pharm Bull,2002,50(7):981-984.
[17] Sannomiya M,Vilegas W,Rastrelli L,et al. A Flavonoid glycoside from maytenus aquifolium[J].Phytochemistry,1998,49(1):237-239.
[18] JIANG C L,Tsai S F,Lee S S,et al. Flavonoids from Curcuma longa leaves and their NMR assignments[J].Nat Prod Commun,2015,10(1):63-66.
[19] XIE C,XU L Z,LUO X Z,et al. Flavonol glycosides from Lysimachia capillipes[J]. J Asian Nat Prod Res,2002,4(1):17-23.
[20] Cristina M,Alessandra B,Sara V,et al. Flavonoid characterization and in vitro antioxidant activity of Aconitum anthora L.(Ranunculaceae)[J].Phytochemistry,2007,69(5):1220-1226.
[21]熊慧,涂楚月,姜海琴,等.过岗龙化学成分分离鉴定[J].中国实验方剂学杂志,2018,24(8):49-53.
[22] Jesús G D,Werner H. Acylated flavonol tetraglycosides from Delphinium gracile[J]. Phytochemistry,2009,71(4):463-468.
[23] HUANG Y J,LU H,YU X L,et al. Dammarane-type triterpenoids from Gentianella azurea[J]. J Nat Prod,2014,77(5):1201-1209.
[2]中国科学院《中国植物志》编辑委员会.中国植物志[M].北京:科学出版社,1989.
[3]田景奎.珍珠菜属两种药用植物化学成分的研究[D].北京:北京协和医学院,2002.
[4]梁冰倩,胡正芳,戚进.湖北麦冬地下部分化学成分[J].中国实验方剂学杂志,2018,24(19):37-41.
[5]刘勇,张琪,陈勐,等.满山香生药学研究[J].时珍国医国药,2015,26(9):2178-2180.
[6]应弘梅,陈润泽,郭达伟,等.细梗香草中皂苷的含量测定及其抗肿瘤作用研究[C]//中国药学会. 2010年中国药学大会暨第十届中国药师周论文集:2010年卷,天津:出版社不详,2010:2672-2679.
[7]程忠哲.细梗香草两个主要抗肿瘤活性皂苷成分的药代动力学研究[D].武汉:华中科技大学,2015.
[8]费正华,陈云亮,马胜林.细梗香草总皂苷诱导肺癌细胞H460凋亡及其机制的研究[J].浙江医学,2014,36(9):742-746.
[9]于淼,冉小库,窦德强,等.孔雀草茎、叶化学成分的分离鉴定[J].中国实验方剂学杂志,2018,24(7):64-68.
[10] Mehdi C,Philippe C,Catherine V S,et al. Acylated flavonol pentaglycosides from Baphia nitida leaves[J].Phytochem Lett,2009,3(2):70-74.
[11] Nabil S,Bernard F,Katia G F,et al. New flavonol tetraglycosides from Astragalus caprinus[J]. Chem Pharm Bull,2002,50(7):981-984.
[12] LIANG B,ZHANG L,TIAN J K. Isolation and characterization of two new saponins from Lysimachia capillipes[J]. Carbohydr Res,2006,341(14):2444-2448.
[13] Bloor S J,LU Q. Cytotoxic saponins from New Zealand Myrsine species[J]. J Nat Prod,1994,57(10):1354-1360.
[14]田景奎,邹忠梅,徐丽珍,等.细梗香草中的两个新三萜皂苷[J].药学学报,2004,39(9):722-725.
[15] Yuko H,Tomoyuki F,Toshiyuki I,et al. Antioxidative properties and flavonoid composition of Chenopodium quinoa seeds cultivated in Japan[J]. Food Chem,2010,119(4):1300-1306.
[16] Semmar N,Fenet B,Gluchoff Fiasson K,et al. New flavonol tetraglycosides from Astragalus caprinus[J].Chem Pharm Bull,2002,50(7):981-984.
[17] Sannomiya M,Vilegas W,Rastrelli L,et al. A Flavonoid glycoside from maytenus aquifolium[J].Phytochemistry,1998,49(1):237-239.
[18] JIANG C L,Tsai S F,Lee S S,et al. Flavonoids from Curcuma longa leaves and their NMR assignments[J].Nat Prod Commun,2015,10(1):63-66.
[19] XIE C,XU L Z,LUO X Z,et al. Flavonol glycosides from Lysimachia capillipes[J]. J Asian Nat Prod Res,2002,4(1):17-23.
[20] Cristina M,Alessandra B,Sara V,et al. Flavonoid characterization and in vitro antioxidant activity of Aconitum anthora L.(Ranunculaceae)[J].Phytochemistry,2007,69(5):1220-1226.
[21]熊慧,涂楚月,姜海琴,等.过岗龙化学成分分离鉴定[J].中国实验方剂学杂志,2018,24(8):49-53.
[22] Jesús G D,Werner H. Acylated flavonol tetraglycosides from Delphinium gracile[J]. Phytochemistry,2009,71(4):463-468.
[23] HUANG Y J,LU H,YU X L,et al. Dammarane-type triterpenoids from Gentianella azurea[J]. J Nat Prod,2014,77(5):1201-1209.