王瑞+師彥平+王慶忠+曹慧
[摘要] 采用正相硅膠柱色譜、重結晶等方法對中藥豨薟草進行了化學成分研究,并運用波譜方法對分離得到的化合物進行了結構鑒定。結果從豨薟草乙酸乙酯部位中分離并鑒定了18個化合物,分別為3,4′-二甲氧基槲皮素(1),3,3′,4′-三甲氧基槲皮素(2),3,3′-二甲氧基槲皮素(3),7,3′,4′-三甲氧基木犀草素(4),烏蘇酸(5),2β,19α-二羥基烏蘇酸(6),2β-羥基烏蘇酸(7),豆甾醇-7-酮(8),3β-羥基-5α,8α-過氧-6,22-麥角甾二烯(9),β-谷甾醇(10),3,3′-二羥基-4,4′-二甲氧基二苯基四氫呋喃駢四氫呋喃木脂素(11),乙酸橙酰胺(12),3-(對甲氧基-間羥基苯基)-N-(2′-對羥基苯乙基)-2E-丙烯酰胺(13),對羥基苯甲醛(14),間羥基對甲氧基苯甲醛(15),3,4,5-三甲氧基苯甲酸(16),丙二酸單乙酯(17),對羥基肉桂酸(18)。其中,化合物1~9,11~18均為首次從該植物中分離得到。
[關鍵詞] 菊科;豨薟草;化學成分
[收稿日期] 2014-08-24
[基金項目] 國家自然科學基金青年基金項目(81303202)
[通信作者] 王瑞,博士,講師,研究方向為天然藥物化學,Tel:(0536)8785288,E-mail:wangrui0810@wfu.edu.cn
豨薟草為常用中藥,別名肥豬草、粘糊菜、黃花仔等。《中國藥典》(2010年版)收載菊科植物豨薟Siegesbeckia orientalis L.,腺梗豨薟S. pubescens Makino和毛梗豨薟S. glabrescens Makino 3種植物的地上部分作為中藥豨薟草入藥[1]。主要分布于江西、湖北、河南、陜西、甘肅等地,具有祛風濕、利筋骨、清熱解毒、降血壓等功能,臨床上用于治療四肢麻痹、高血壓、風濕性關節(jié)炎等癥。目前已經分離得到的化學成分主要為二萜類和倍半萜類[2-4]。鑒于其生物活性多樣的特征,作者對中藥豨薟草的乙酸乙酯萃取部位進行了化學成分的研究,從中分離并鑒定了18個化合物,其中化合物1~9,11~18均為首次從該植物中分離得到。
1 材料
Varian INOVA-400MHz和Varian INOVA-300 MHz超導核磁共振波譜儀,TMS為內標;X-5型顯微熔點測定儀;WFH-203(ZF-1) 三用紫外分析儀;METTLER-AE100電子分析天平;柱色譜及薄層色譜硅膠為青島海洋化工集團有限公司產品;所用溶劑為分析純。藥材購買自蘭州黃河藥材市場,樣品由中國科學院蘭州化學物理研究所西部特色植物資源化學重點實驗室戚歡陽副研究員鑒定為腺梗豨薟,植物藥材標本存貯于甘肅省天然藥物重點實驗室,編號為No. ZY2007S001。
2 提取和分離
將中藥豨薟草9 kg粉碎后,用95%乙醇熱回流提取3次(3 h/次),合并提取液,減壓濃縮得總浸膏800 g,以水混懸,依次用石油醚、乙酸乙酯、正丁醇萃取,減壓濃縮得各部分浸膏。取乙酸乙酯浸膏120 g,經硅膠柱色譜分離,以石油醚:丙酮(30∶1~0∶1)進行梯度洗脫,根據(jù)薄層檢測結果合并相同餾分,共得到7個不同極性段組分:A(30∶1),B(15∶1),C(8∶1),D(4∶1),E(2∶1),F(xiàn)(1∶1),G(0∶1)。粗分離過程中,通過對不同極性段析出的晶體和固體粉末進行重結晶,分離得到化合物5(30 mg)和10(140 mg)。組分B經硅膠柱色譜,以石油醚-乙酸乙酯(30∶1)和石油醚-丙酮(30∶1)作為洗脫劑反復洗脫,得到化合物8(13 mg)。組分C經硅膠柱色譜,以石油醚-乙酸乙酯(20∶1)為洗脫劑洗脫,得到3個流分C1~C3,各流分經硅膠柱色譜反復分離,得到化合物9(10 mg),12(23 mg)和15(5.2 mg),14(6.7 mg),16(8.5 mg),18(6.5 mg)和4(10 mg);組分D經硅膠柱色譜,以石油醚-乙酸乙酯(15∶1)為洗脫劑洗脫,得到4個部分D1~D4;D2部分經硅膠柱色譜,以石油醚-乙酸乙酯(15∶1),氯仿-乙酸乙酯(15∶1)和石油醚-丙酮-冰醋酸(15∶1∶0.1)為洗脫劑反復洗脫,得到化合物2(6.7 mg)和7(7.2 mg);同樣的方法從D3和D4部分中分離得到化合物1(15 mg),3(5.5 mg),6(6.3 mg),11(11.8 mg)和17(8.5 mg)。組分E經硅膠柱色譜反復分離純化,結合重結晶,分離得到化合物13(16.5 mg)。
3 結構鑒定
化合物1 黃色粉末狀固體;1H-NMR(acetone-d6,400 MHz)δ: 12.2(1H,s,5-OH),7.14(1H,d,J=2.0 Hz,H-1′),7.03(1H,dd,J=8.4,2.0 Hz,H-6′),6.46(1H,d,J=8.4 Hz,H-5′),6.24(1H,s,H-6),5.91(1H,s,H-8),3.41(3H,s,4′-OMe),3.35(3H,s,3-OMe); 13C NMR(acetone-d6,100 MHz); δ: 178.0(s,C-4),165.1(s,C-7),160.9(s,C-5),156.2(s,C-9),155.9(s,C-2),148.8(s,C-4′),145.2(s,C-3′),137.8(s,C-3),120.7(s,C-1′),120.6(d,C-6′),115.7(d,C-2′),115.5(d,C-5′),105.1(s,C-10),97.7(d,C-6),92.2(d,C-8),59.6(q,3-OMe),56.0(q,4′-OMe)。以上數(shù)據(jù)與文獻[5]對照,鑒定該化合物為3,4′-二甲氧基槲皮素(3,4′-dimethoxy quercetin)。endprint
化合物2 黃色粉末狀固體;1H-NMR(acetone-d6,300 MHz)δ: 7.75(1H,d,J=1.8 Hz,H-1′),7.73(1H,m,H-6′),6.46(1H,d,J=8.7 Hz,H-5′),6.50(1H,s,H-6),6.26(1H,s,H-8),3.91(3H,s,4′-OMe),3.90(3H,s,3′-OMe),3.86(3H,s,3-OMe); 13C-NMR(acetone-d6,75 MHz)δ: 179.4(s,C-4),165.0(s,C-7),162.7(s,C-5),157.8(s,C-9),156.4(s,C-2),152.6(s,C-4′),149.9(s,C-3′),139.4(s,C-3),123.6(s,C-1′),122.9(d,C-6′),112.5(d,C-2′),112.2(d,C-5′),105.6(s,C-10),99.3(d,C-6),94.5(d,C-8),60.3(q,3-OMe),56.2(q,3′-OMe),56.0(q,4′-OMe)。以上數(shù)據(jù)與文獻[6]對照,鑒定該化合物為3,3′,4′-三甲氧基斛皮素(3,3′,4′-trimethoxy quercetin)。
化合物3 黃色粉末狀固體;1H-NMR(DMSO-d6,400 MHz)δ:12.6(1H,s,5-OH),7.56(1H,m,H-6′),7.54(1H,d,J=2.0 Hz,H-1′),7.15(1H,d,J=9.2 Hz,H-5′),6.43(1H,d,J=2.0 Hz,H-6),6.21(1H,d,J=2.0 Hz,H-8),3.87(3H,s,3′-OMe),3.79(3H,s,3-OMe); 13C-NMR(DMSO-d6,100 MHz)δ:177.9(s,C-4),164.2(s,C-7),161.3(s,C-5),156.4(s,C-9),155.3(s,C-2),150.2(s,C-4′),146.3(s,C-3′),137.9(s,C-3),122.3(s,C-1′),120.3(d,C-6′),114.9(d,C-2′),111.9(d,C-5′),104.2(s,C-10),98.5(d,C-6),93.6(d,C-8),59.7(q,3-OMe),55.6(q,3′-OMe)。以上數(shù)據(jù)與文獻[7]對照,鑒定該化合物為3,3′-二甲氧基斛皮素(3,3′-dimethoxy quercetin)。
化合物4 黃色粉末狀固體;1H-NMR(CDCl3,300 MHz)δ:12.63(1H,s,5-OH),7.73(1H,d,J=2.4 Hz,H-2′),7.71(1H,m,H-6′),6.96(1H,d,J=9 Hz,H-5′),6.44(1H,d,J=1.8 Hz,H-6),6.35(1H,d,J=1.8 Hz,H-8),5.73(1H,s,H-3),3.98(3H,s,7-OMe),3.87(6H,s,3′,4′-OMe); 13C-NMR(CDCl3,100 MHz)δ:178.8(s,C-4),165.4(s,C-7),161.9(s,C-2),156.7(s,C-5),155.6(s,C-9),148.7(s,C-4′),145.5(s,C-3′),123.6(s,C-1′),121.5(d,C-6′),114.4(d,C-2′),114.4(d,C-5′),110.3(s,C-10),106.1(s,C-3),97.8(d,C-6),92.1(d,C-8),60.1(q,7-OMe),56.0(q,4′-OMe),55.6(q,3′-OMe)。以上數(shù)據(jù)與文獻[8]對照,鑒定該化合物為7,3′,4′-三甲氧基木犀草素(7,3′,4′-trimethoxy luteolin)。
化合物5 無色針狀晶體;13C-NMR(DMSO-d6,100 MHz)δ: 178.2(s,C-28),138.1(s,C-13),124.5(d,C-12),76.8(d,C-3),54.7(s,C-5),52.3(d,C-18),46.9(s,C-17),46.8(d,C-9),41.6(s,C-14),39.8(s,C-8),38.5(d,C-20),38.4(d,C-19),38.3(s,C-4),38.2(t,C-1),36.5(s,C-10),36.3(t,C-22),32.7(t,C-7),30.1(t,C-15),28.9(t,C-21),28.2(q,C-23),27.5(t,C-2),23.7(t,C-11),23.2(q,C-27),22.8(t,C-16),21.0(q,C-30),17.9(t,C-6),16.9(q,C-29),16.8(q,C-26),16.0(q,C-25),15.2(q,C-24)。以上數(shù)據(jù)與文獻[9]對照,鑒定該化合物為烏蘇酸(ursolic acid)。
化合物6 白色針狀晶體;13C-NMR(acetone-d6,75 MHz)δ: 178.5(s,C-28),139.1(s,C-13),128.1(d,C-12),78.6(d,C-3),72.5(s,C-19),65.6(d,C-2),53.8(d,C-18),48.2(d,C-5),47.7(s,C-17),47.2(d,C-9),41.9(d,C-20),41.9(t,C-1),41.7(s,C-14),40.2(s,C-8),38.3(s,C-4),38.2(s,C-10),37.9(t,C-22),33.1(t,C-7),29.1(q,C-30),26.5(q,C-23),26.4(t,C-21),25.7(t,C-16),24.1(q,C-27),23.7(t,C-11),21.7(q,C-29),18.3(t,C-6),16.8(q,C-26),16.2(q,C-25),16.0(q,C-24)。以上數(shù)據(jù)與文獻[10]對照,鑒定該化合物為2β,19α-二羥基烏蘇酸(2β,19α-dihydroxyursolic acid)。endprint
化合物7 白色針狀晶體;13C-NMR(acetone-d6,75 MHz)δ:178.5(s,C-28),138.8(s,C-13),127.2(d,C-12),78.6(d,C-3),65.6(d,C-2),53.2(d,C-18),48.3(d,C-5),47.6(s,C-17),46.3(d,C-9),42.4(t,C-1),39.9(s,C-14),39.8(s,C-8),39.3(d,C-20),39.2(d,C-19),38.3(s,C-4),37.0(s,C-10),33.8(t,C-22),33.2(t,C-7),32.0(t,C-15),28.8(t,C-21),28.1(q,C-23),27.7(t,C-2),25.1(t,C-11),23.3(q,C-27),22.7(t,C-16),20.9(q,C-30),18.1(t,C-6),17.1(q,C-29),16.9(q,C-26),16.3(q,C-25),16.2(q,C-24)。以上數(shù)據(jù)與文獻[10]對照,鑒定該化合物為2β-羥基烏蘇酸(2β-hydroxyursolic acid)。
化合物8 無色針狀晶體;1H-NMR(CDCl3,400 MHz)δ: 5.69(1H,s,H-6),3.67(1H,m,H-3),1.20(3H,s,H-19),0.93(3H,d,J=6.6 Hz,H-21),0.85(3H,t,J=6.9 Hz,H-29),0.84(3H,d,J=6.3 Hz,H-26),0.82(3H,d,J=6.3 Hz,H-27),0.69(3H,s,H-18);13C-NMR(CDCl3,100 MHz)δ: 36.6(t,C-1),31.0(t,C-2),70.5(d,C-3),41.7(t,C-4),165.0(s,C-5),126.1(d,C-6),202.2(s,C-7),45.3(d,C-8),49.8(d,C-9),38.2(s,C-10),21.1(t,C-11),38.6(t,C-12),43.0(s,C-13),49.8(d,C-14),26.3(t,C-15),28.5(t,C-16),54.7(d,C-17),11.9(q,C-18),17.2(q,C-19),36.0(d,C-20),18.8(q,C-21),138.1(d,C-22),129.4(d,C-23),45.7(d,C-24),29.0(d,C-25),19.0(q,C-26),19.8(q,C-27),22.9(t,C-28),11.9(q,C-29)。以上數(shù)據(jù)與文獻[11]對照,鑒定該化合物為豆甾醇-7-酮(stigmasterol-7-one)。
化合物9 無色針狀晶體;1H-NMR(CDCl3,300 MHz)δ: 6.50(1H,d,J=8.4 Hz,H-7),6.24(1H,d,J=8.4 Hz,H-6),5.22(1H,m,H-22),5.14(1H,m,H-23),3.97(1H,m,H-3),1.01(3H,d,J=7.2 Hz,H-28),0.90(3H,d,J=6.6 Hz,H-21),0.88(3H,s,H-19),0.82(3H,s,H-18),0.73(3H,d,J=6.6 Hz,H-27); 13C-NMR(CDCl3,75 MHz)δ:37.0(t,C-1),30.1(t,C-2)66.5(d,C-3),34.7(t,C-4),79.4(s,C-5),130.7(d,C-6),135.4(d,C-7),82.1(s,C-8),51.1(d,C-9),36.9(s,C-10),20.6(t,C-11),39.3(t,C-12),44.6(s,C-13),51.7(d,C-14),28.6(t,C-15),23.4(t,C-16),56.2(d,C-17),12.9(q,C-18),18.2(q,C-19),39.7(d,C-20),19.6(q,C-21),132.3(d,C-22),135.2(d,C-23),42.8(d,C-24),33.1(d,C-25),19.9(q,C-26),20.9(q,C-27),17.5(q,C-28)。以上數(shù)據(jù)與文獻[12]對照,鑒定該化合物為3β-羥基-5α,8α-過氧-6,22-麥角甾二烯(5α,8α-epidioxy-24(R)-methyl- cholesta-6,22-diene-3β-ol)。
化合物10 無色針狀結晶;mp 136~137 ℃,與β-谷甾醇[13]對照品在多種溶劑系統(tǒng)展開進行TLC 對照,Rf值及顯色行為一致,且混合熔點不下降,故鑒定化合物10為β-谷甾醇(β-sitosterol)。
化合物11 無色針狀晶體;1H-NMR(CDCl3,400 MHz)δ: 6.90(2H,d,J=1.6 Hz,H-2,2′),6.89(2H,d,J=8.0 Hz,H-5,5′),6.82(2H,dd,J=8.0,1.6 Hz,H-6,6′),4.74(2H,d,J=4.4 Hz,H-7,7′),4.25(2H,dd,J=9.2 Hz,H-9a,9′a),3.88(2H,dd,J=9.6,4.0 Hz,H-9b,9′b),3.91(6H,s,OMe),3.10(2H,m,H-8,8′); 13C-NMR(CDCl3,100 MHz)δ: 146.7(s,C-4,4′),145.2(s,C-3,3′),132.9(s,C-1,1′),118.9(d,C-6,6′),114.3(d,C-2,2′),108.6(d,C-5,5′),85.8(d,C-8,8′),71.6(t,C-7,7′),55.9(q,2×OMe),54.2(d,C-9,9′)。以上數(shù)據(jù)與文獻[14]對照,鑒定該化合物為3,3′-二羥基-4,4′-二甲氧基二苯基四氫呋喃駢四氫呋喃木脂素(2,6-di(3-hydroxy-4- methoxyphenyl)- 3,7-dioxacyclo[3.3.0]octane)。endprint
化合物12 白色針狀晶體;1H-NMR(CDCl3,400 MHz)δ:6.78(1H,d,J=7.6 Hz,8-NH),6.04(1H,d,J=8.4 Hz,5-NH),4.78(1H,m,H-7,4.35(1H,m,H-4),3.93(1H,dd,J=11.2,4.8 Hz,H-3a),3.82(1H,dd,J=11.2,4.4 Hz,H-3b),3.22(1H,dd,J=14.0,6.0 Hz,H-10a),3.07(1H,dd,J=13.6,8.4 Hz,H-10b),2.75(2H,m,H-11); 13C-NMR(CDCl3,100 MHz)δ:20.8(q,C-1),170.7(s,C-2),64.5(t,C-3),49.4(d,C-4),170.2(s,C-6),54.9(d,C-7),167.1(s,C-9),38.4(t,C-10),37.4(t,C-11),136.7(s,C-1),136.6(s,C-1′),133.6(s,C-1″),131.9(d,C-4″),127.1(d,C-4),126.7(d,C-4′),127.0(d,C-2″,6″)。以上數(shù)據(jù)與文獻[15]對照,鑒定該化合物為乙酸橙酰胺(aurantiamide acetate)。
化合物13 無色針狀晶體;1H-NMR(DMSO-d6,300 MHz)δ:8.01(1H,t,J=6.0 Hz,NH),7.32(1H,d,J=15.3 Hz,H-2),7.11(1H,d,J=1.8 Hz,H-5),7.01(2H,d,J=8.1 Hz,H-4′,8′),6.98(1H,m,H-9),6.79(1H,d,J=7.5 Hz,H-8),6.68(2H,d,J=8.1 Hz,H-5′,7′),6.44(1H,d,J=15.6 Hz,H-3),3.34(2H,m,H-1′),2.65(2H,t,J=7.5 Hz,H-2′); 13C-NMR(DMSO-d6,75 MHz)δ:165.4(s,C-1),155.7(s,C-6′),148.3(s,C-7),147.8(s,C-6),138.9(d,C-3),129.6(d,C-4′,8′),126.5(s,C-4),121.6(d,C-9),119.0(d,C-2),115.7(d,C-5),115.2(d,C-5′,7′),110.7(d,C-8),55.5(q,OMe),40.7(t,C-1′),34.5(t,C-2′)。以上數(shù)據(jù)與文獻[16]對照,鑒定該化合物為3-(對甲氧基-間羥基苯基)-N-(2′-對羥基苯乙基)-2E-丙烯酰胺[3-(m-hydroxyl-p- methoxy)-N-(2′-p-hydroxylphenethyl)-2E-acrylamide]。
化合物14 淡黃色針狀晶體;1H-NMR(acetone-d6,300 MHz)δ:9.85(1H,s,CHO),9.40(1H,brs,OH),7.81(2H,d,J=8.4 Hz,H-3,5),7.01(2H,d,J=8.4 Hz,H-2,4); 13C-NMR(acetone-d6,75 MHz)δ: 189.8(d,CHO),162.6(s,C-1),131.6(d,C-2,4),115.5(s,C-3,5)。以上數(shù)據(jù)與文獻[17]對照,鑒定該化合物為對羥基苯甲醛(p-hydroxy benzaldehyde)。
化合物15 淡黃色針狀晶體;1H-NMR(CDCl3,300 MHz)δ:9.83(1H,s,4-CHO),7.43(1H,dd,J=8.7,1.8 Hz,H-5),7.42(1H,d,J=1.8 Hz,H-6),7.05(1H,d,J=8.7 Hz,H-3),6.24(1H,br s,2-OH),3.97(3H,s,1-OMe); 13C-NMR(CDCl3,75 MHz)δ:190.9(d,CHO),151.6(s,C-1),147.1(s,C-2),129.8(s,C-4),127.5(d,C-5),114.3(d,C-6),108.7(d,C-3),56.1(q,1-OMe)。 以上數(shù)據(jù)與文獻[18]對照,鑒定該化合物為間羥基對甲氧基苯甲醛(m-hydroxy-p-methoxy benzaldehyde)。
化合物16 無色針狀晶體;1H-NMR(CDCl3,400 MHz)δ:7.36(2H,s,H-2,6),3.95(3H,s,4-OMe),3.92(6H,s,3,5-OMe);13C-NMR(CDCl3,100 MHz)δ: 171.6(s,COOH),152.9(s,C-3,5),143.0(s,C-4),123.9(s,C-1),107.4(d,C-2,4),60.9(q,4-OMe),56.2(q,3,5-OMe)。以上數(shù)據(jù)與文獻[19]對照,鑒定該化合物為3,4,5-三甲氧基苯甲酸(3,4,5-trimethoxybenzoic acid)。endprint
化合物17 無色針狀晶體;1H-NMR(CDCl3,400 MHz)δ: 4.24(2H,q,J=7.2 Hz,H-1′),3.45(2H,s,H-2),1.31(3H,t,J=7.2 Hz,H-2′);13C-NMR(DEPT)(CDCl3,100 MHz)δ:171.4(s,C-3),166.9(s,C-1),61.9(t,C-1′),40.8(t,C-2),13.9(q,C-2′)。以上數(shù)據(jù)與文獻[20]對照,鑒定該化合物為丙二酸單乙酯(Monoethyl malonate)。
化合物18 淡黃色針狀晶體;1H-NMR(CDCl3,400 MHz)δ:7.57(1H,d,J=16.0 Hz,H-7),7.51(1H,d,J=8.4 Hz,H-2,6),6.87(1H,d,J=8.4 Hz,H-3,5),6.30(1H,d,J=16.0 Hz,H-8);13C-NMR(DEPT)(CDCl3,100 MHz)δ:168.0(s,C-9),160.1(s,C-4),144.9(s,C-1),130.2(d,C-2,4),126.2(d,C-7),116.0(d,C-3. 5),115.1(d,C-8)。以上數(shù)據(jù)與文獻[21]對照,鑒定該化合物為對羥基肉桂酸(p-hydroxylcinnamic acid)。
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Chemical constituents from traditional Chinese medicine
Siegesbeckia pubescens
WANG Rui, SHI Yan-ping, WANG Qing-zhong, CAO Hui
(1.Key Laboratory of Biochemistry and Molecular Biology in Universities of Shandong Province, Weifang University, Weifang 261061, China;
2. Key Laboratory of Chemistry of Northwestern Plant Resources and Key Laboratory for Natural Medicine of Gansu Province,
Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China)
[Abstract] Column chromatography on silica gel was used to study the chemical constituents of traditional Chinese medicine Siegesbeckia pubescens. The chemical structures of the separated compounds were elucidated by spectroscopic data analyses. As a result, eighteen compounds were obtained and identified as 3, 4′-dimethoxy quercetin(1), 3, 3′, 4′-trimethoxy quercetin(2), 3, 3′-dimethoxy quercetin(3), 7, 3′, 4′-trimethoxy luteolin(4), ursolic acid(5), 2β,19α-dihydroxyursolic acid(6), 2β-hydroxyursolic acid(7), stigmasterol-7-one(8), 5α, 8α-epidioxy-24(R)-methyl-cholesta-6, 22-diene-3β-ol(9), β-sitosterol(10), 2, 6-di(3-hydroxy-4-methoxyphenyl)- 3, 7-dioxacyclo[3.3.0]octane(11), aurantiamide acetate(12),3-(m-hydroxyl-p- methoxy)-N-(2′-p-hydroxylphenethyl)-2E-acrylamide(13), p-hydroxy benzaldehyde(14), m-hydroxy-p-methoxy benzaldehyde(15), 3, 4, 5-trimethoxybenzoic acid(16), monoethyl malonate(17), and p-hydroxylcinnamic acid(18). Among them, compounds 1-9, 11-18 were isolated from this plant for the first time.
[Key words] Compositae; Siegesbeckia pubescens; chemical constituents
doi:10.4268/cjcmm20142422
[責任編輯 丁廣治]endprint