胡祖艳,范青飞,张玉梅,冯 峰,杨俊林,宋启示*
1中国科学院西双版纳热带植物园热带植物资源可持续利用重点实验室,昆明 650223;2中国科学院大学,北京 100049;3 昆明理工大学,昆明 650093
青脆枝[1]学名为臭味假柴龙树[NothapodytesnimmonianaGraham,又名Nothapodytesfoetida(Wight)Sleumer 或者MappiafoetidaMeirs],为茶茱萸科假柴龙树属植物,分布于印度、斯里兰卡、缅甸、泰国、柬埔寨、印度尼西亚(苏门塔腊)、菲律宾(吕宋)、日本琉球群岛至我国台湾。青脆枝入药有抗癌、祛风除湿、理气散寒等作用,全株含喜树碱。自20 世纪70年代开始,已有很多外国科研工作者对青脆枝进行了研究,分离到的化合物主要为喜树碱及其衍生物[2-8],研究的植物主要采于印度等地区,而国内对青脆枝的研究较少,特别是对生长于中国大陆的青脆枝的研究。由于地域及生长环境的不同,植物中所含的化学成分可能不同。因此本文以生长于中国大陆的青脆枝为对象,对其化学成分进行研究,分离鉴定了19 个化合物。分别为:香树精(1)、7-酮基-β-谷甾醇(2)、豆甾醇(3)、谷甾-5-烯-3β,7β-二醇(4)、丙氧基香树精(5)、鹅掌楸碱(6)、松柏苷(7)、丁香酸葡萄糖苷(8)、丁香苷(9)、咖啡酸(10)、6,7-二羟基香豆素(11)、(3R)-3,6,7 三甲基十九碳酸甲酯(12)、喜树碱(13)、9-甲氧基喜树碱(14)、10-羟基喜树碱(15)、麦黄酮(16)、豆甾-5-烯-3β,7α-二醇(17)、胡萝卜苷(18)、谷甾醇(19)。其中化合物1~12 均为首次从该植物中分离得到。
熔点在XTRC-1 显微熔点测定仪上测定;核磁共振谱用Bruker AV-400、DRX-500 及AvanceⅢ-600超导核磁共振仪测定,TMS 为内标;EI-MS 用Waters AutoSpec Premier P776 双聚焦三扇形磁质谱仪测定;柱层析硅胶(200~300 目)及薄板层析硅胶(GF-254)均为青岛海洋化工厂生产;MCI 为日本三菱化学株式会社生产;凝胶材料使用GE Healthcare 的Sephadex LH -20。所用有机试剂均为分析纯。
青脆枝(N.nimmoniana)小枝于2012年3月采于云南省西双版纳傣族自治州勐腊县勐伴,并由中国科学院西双版纳热带植物园王洪高级工程师鉴定,标本存放于中国科学院西双版纳热带植物园民族药研究组实验室。
将青脆枝小枝晾干,粉碎,称重得62 kg。用90%甲醇热回流提取3 次(4、3、3 h)。合并提取液,减压浓缩得甲醇浸膏6775 g。将取6000 g 浸膏用水搅拌溶解稀释后依次用石油醚、氯仿、正丁醇萃取,每种溶剂萃取3 次,得到石油醚萃取物521 g,氯仿萃取物335 g,正丁醇萃取物494 g。石油醚部分经硅胶柱(200~300 目)分离,以石油醚-丙酮梯度洗脱(90∶10、80∶20、70∶30、60∶40、50∶50、0∶100)得到6 个组份(A1-A6);A4 经反复硅胶柱层析和Sephadex LH-20 纯化,得到化合物3(20 mg)、18(15 mg)、19(20 mg);A5 经反复硅胶柱层析和Sephadex LH-20 纯化,得到化合物1(17 mg)、5(13 mg);氯仿部分经硅胶柱(200~300 目)分离,以石油醚-丙酮(90∶10、70∶30、60∶40、50∶50、30∶70、0∶100)梯度洗脱,得到B1-B6 六个组分;B1 经反复硅胶柱层析,MCI 和Sephadex LH-20 纯化,得到化合物16(28 mg);B3 经反复硅胶柱层析,MCI 和Sephadex LH-20纯化,得到化合物4(29 mg)、17(30 mg);B4 经反复硅胶柱层析,MCI 和Sephadex LH-20 纯化,得到化合物13(20 mg)、12(11 mg);B5 经反复硅胶柱层析,MCI 和Sephadex LH-20 纯化,得到化合物2(31 mg);正丁醇部分上大孔树脂分段,分别以20%、40%、60%、80%、100%比例的甲醇/水溶液和丙酮梯度洗脱得到六个组份(C1-C6);C1 经反复MCI 柱层析和Sephadex LH-20 纯化,得到化合物14(40 mg),15(18 mg);C2 经反复MCI 柱层析和Sephadex LH-20 纯化,得到化合物6(16 mg)、7(19 mg);C3经反复MCI 柱层析和Sephadex LH-20 纯化,得到化合物8(13 mg)、9(20 mg);C4 经反复MCI 柱层析和Sephadex LH-20 纯化,得到化合物10(22 mg)、11(10 mg)。
化合物1 白色粉末 mp.187~190 ℃;分子式为C30H50O;EI-MSm/z426[M]+;1H NMR (CDCl3,400 MHz)δ:0.79(3H,s),0.83(3H,s),0.87 (3H,s),0.93 (3H,s),0.96 (3H,s),1.00 (3H,s),1.13(3H,s),3.22(1H,m,H-2),5.18 (1H,t,J=6.9Hz,H-12);13C NMR (CDCl3,100 MHz)δ:38.8(C-1),27.2 (C-2),79.3 (C-3),39.0 (C-4),55.4(C-5),18.6 (C-6),32.8 (C-7),40.0 (C-8),47.9(C-9),37.2 (C-10),23.8 (C-11),121.9 (C-12),145.5 (C-13),41.9 (C-14),28.7 (C-15),26.3 (C-16),32.9 (C-17),47.5 (C-18),47.1 (C-19),31.4(C-20),34.9 (C-21),37.4 (C-22),28.4 (C-23),15.9 (C-24),15.8(C-25),17.1(C-26),26.4 (C-27),27.5(C-28),33.6(C-29),23.9 (C-30)。以上数据与文献[9]报道一致,因此确定化合物1 为香树精(β-amyrin)。
化合物2 白色粉末 mp.120~123 ℃;分子式为C29H48O2;1H NMR (CDCl3,500 MHz)δ:3.70(1H,t,J=11.0 Hz,H-3),2.53 (1H,d,J=13.6 Hz,H-4a),2.42 (1H,t,J=11.7 Hz,H-4b),5.72(1H,s,H-6),2.27 (1H,t,J=11.5 Hz,H-8),2.06(1H,dt,J=12.9 Hz,H-12b),0.71 (3H,s,H-18),1.22 (3H,s,H-19),0.94 (3H,d,J=6.2 Hz,H-21),0.83 (3H,d,J=6.2 Hz,H-26),0.87 (3H,d,J=6.2Hz,H-27),0.84 (3H,t,J=6.2 Hz,H-29);13C NMR (CDCl3,126 MHz)δ:36.6 (C-1),31.4(C-2),70.8 (C-3),42.0 (C-4),165.3 (C-5),126.4 (C-6),202.6 (C-7),45.6 (C-8),50.2 (C-9,C-14),38.5 (C-10),21.4 (C-11),38.9 (C-12),43.3 (C-13),26.5 (C-15),28.8 (C-16),54.9 (C-17),12.2 (C-18,C-29),17.5 (C-19),36.3 (C-20),19.1 (C-21),34.2 (C-22),26.3 (C-23),46.0(C-24),29.3 (C-25),19.3 (C-26),20.0(C-27),23.3(C-28)。以上数据与文献[10]报道基本一致,因此确定化合物2 为7-酮基-β-谷甾醇(7-keto-β-sitosterol)。
化合物3 白色片状结晶 mp.169~170 ℃,分子式为C29H48O;EI-MSm/z412[M]+。其在TLC(展开系统:氯仿/丙酮:12∶1、10∶1、8∶1;石油醚/丙酮:15∶1、10∶1、7∶1)上的斑点位置及显色与豆甾醇标准品的相同,且与标准品混合熔点不下降,因此确定化合物3 为豆甾醇。因此确定化合物3 为豆甾醇(stigmasterol)。
化合物4 白色粉末 mp.157~158 ℃;分子式为C29H50O2;EI-MSm/z430 [M]+;1H NMR(CH3OD,400 MHz)δ:3.59 (1H,m,H-3),5.60(1H,brs,H-6),3.85 (1H,brs,J=7.6Hz,H-7),0.69 (3H,s,H-18),1.07 (3H,s,H-19),0.99 (3H,d,J=6.4 Hz,H-21),0.83 (3H,d,J=7.6 Hz,H-26),0.79 (3H,d,J=7.2 Hz,H-27),0.87(3H,t,J=6.6 Hz,H-29);13C NMR (CH3OD,100 MHz)δ:37.1 (C-1),31.8 (C-2),71.5(C-3),41.9 (C-4),143.7(C-5),125.6 (C-6),73.6 (C-7),39.8 (C-8),48.4 (C-9),36.6 (C-10),21.3 (C-11),41.1(C-12),43.1 (C-13),56.2 (C-14),26.6 (C-15)28.8 (C-16),55.6 (C-17),12.0 (C-18),19.0 (C-19),36.3 (C-20),19.2 (C-21),32.1 (C-22),29.9(C-23),46.0 (C-24),26.3 (C-25),19.4 (C-26),20.0 (C-27),22.9 (C-28),12.2 (C-29)。以上数据与文献[11]报道一致,因此确定化合物4 为谷甾-5-烯-3β,7β-二醇(stigmast-5-en-3β,7β-diol)。
化合物5 白色粉末 分子式为C33H56O;EI-MSm/z468 [M]+;1H NMR (CDCl3,500 MHz)δ:0.77,0.83,0.87,0.93,0.99,1.07,1.27 (21H,s,7×-CH3),1.53 (3H,s,H-OCH2CH2CH3),2.17(2H,m,H-OCH2CH2CH3),3.16 (1H,dd,J=25.7,16.1 Hz,H-3),3.55 (2H,q,J=6.6 Hz,-OCH2CH2CH3),5.12 (1H,t,J=5.4 Hz,H-12);13C NMR (CDCl3,126 MHz)δ:38.9 (C-1),27.1 (C-2),79.1 (C-3),38.9 (C-4),55.3 (C-5),18.5 (C-6),32.8 (C-7),38.8 (C-8),47.8 (C-9),36.2 (C-10),23.6 (C-11),121.9 (-12),145.3 (C-13),41.9(C-14),26.2 (C-15),27.1 (C-16),32.6 (C-17),47.3 (C-18),46.9 (C-19),31.2 (C-20),34.8 (C-21),37.1 (C-22),28.2 (C-23),15.6 (C-24),15.7(C-25),16.9 (C-26),26.1 (C-27),28.5 (C-28),33.4 (C-29),23.7 (C-30),62.9 (C-1'),25.9 (C-2'),14.2 (C-3')。以上数据与文献[12]报道基本一致,因此确定化合物5 为丙氧基香树精(propyloxyamyrin)。
化合物6 白色粉末 分子式为C34H46O18;1H NMR (Pyridine-d5,400 MHz)δ:3.73 (12H,s,4 ×OCH3),5.80 (两个端基氢,d,J=7.3Hz),6.88(4H,s,H-2',6',2'',6'');13C NMR (Pyridine-d5,100 MHz)δ:57.0 (4C,4 × OCH3),55.2(2C,C-1,5),86.5 (2C,C-2,6),72.6(2C,C-4,8),135.9 (2C,C-1',1''),105.3(4C,C-2',6',2'',6''),154.3 (4C,C-3',5',3'',5''),138.6(2C,C-4',4''),105.2(2C,C-1-Glc),(2C,C-2-Glc),78.8 (2C,C-3-Glc),76.571.9 (2C,C-4-Glc),79.2 (2C,C-5-Glc),62.9(2C,C-6-Glc)。以上数据与文献[13]报道基本一致,所以确定化合物6 为鹅掌楸碱(liriodendrin)。
化合物7 白色粉末 分子式为C16H22O8;EI-MSm/z342 [M]+;1H NMR (CH3OD,400MHz)δ:3.89(3H,s,-OCH3),7.09 (1H,d,J=1.9 Hz,H-2),7.12 (1H,d,J=8.4 Hz,H-5),6.95 (1H,dd,J=8.3,1.6 Hz,H-6),6.54 (1H,d,J=15.8 Hz,H-7),6.29 (1H,dt,J=15.8,5.7 Hz,H-8),4.23(2H,d,J=5.7 Hz,H-9a,9b),4.91 (1H,d,J=7.8 Hz,H-1-Glc);13C NMR (CH3OD,100MHz)δ:56.6(C-OCH3),133.6 (C-1),111.3(C-2),151.1(C-3),147.6 (C-4),117.8(C-5),120.7(C-6),131.2 (C-7),128.8(C-8),62.4 (C-9),102.7 (C-1'),74.9 (C-2'),77.8 (C-3'),71.3 (C-4'),78.2(C-5'),63.7(C-6')。以上数据与文献[14]报道一致,因此确定化合物7 为松柏苷(coniferin)。
化合物8 白色粉末 分子式为C15H20O10;EIMSm/z360 [M]+;1H NMR (CH3OD,400MHz)δ:3.90 (6H,s,2 × OCH3),7.36 (2H,s,H-2,6),5.08 (1H,d,J=7.0 Hz,H-1'),3.78 (1H,dd,J=12.0,5.5 Hz,H-6' a),3.67 (1H,dd,J=12.0,5.5 Hz,H-6'b);13C NMR (CH3OD,100 MHz)δ:57.1(C-OCH3),127.9 (C-1),154.2 (C-3,5),108.7(C-2),140.1(C-4),169.5(C-COOH),104.6(C-1'),75.8 (C-2'),78.6(C-3'),71.4 (C-4'),77.9 (C-5'),62.6(C-6')。以上数据与文献[15]报道一致,因此确定化合物8 为丁香酸葡萄糖苷(glucosyringic acid)。
化合物9 白色粉末 mp.210 ℃;分子式为C17H24O9;EI-MSm/z372[M]+;1H NMR (CH3OD,600 MHz)δ:3.76 (6H,s,-OCH3),6.76 (2H,H-2,6),6.56 (1H,d,J=15.9Hz,H-7),6.33 (1H,td,J=15.9,10.8,5.4 Hz,H-8),4.22 (2H,dd,J=5.4,1.5 Hz,H-9),4.88 (1H,d,J=7.2 Hz,H-1'),3.22~3.43 (4H,m,H-2',3',4',5'),3.67 (1H,dd,J=12.0,4.0 Hz,H-6'),3.80 (1H,dd,J=12.0,2.0 Hz,H-6');13C NMR(CH3OD,151 MHz)δ:57.1 (-OCH3),135.9 (C-1),154.5 (C-2,6),105.5 (C-3,5),135.4 (C-4),131.4 (C-7),130.1 (C-8),63.7(C-9),105.4 (C-1'),75.8 (C-2'),78.5 (C-3'),71.4 (C-4'),77.9 (C-5'),62.7 (C-6')。以上数据与文献[16]报道一致,因此确定化合物9 为丁香苷(syringin)。
化合物10 白色粉末 分子式为C9H8O4;EI-MSm/z180 [M]+;1H NMR (CH3OH,600 MHz)δ:6.23 (1H,d,J=15.8 Hz,H-8),6.76 (1H,d,J=8.6 Hz,H-5),6.92 (1H,dd,J=2.1,8.4 Hz,H-6),7.03 (1H,d,J=2.2 Hz,H-2),7.54 (1H,d,J=15.8 Hz,H-7);13C NMR (CH3OH,151 MHz,)δ:127.9 (C-1),115.2 (C-2),146.9 (C-3),149.6 (C-4),116.6 (C-5),123.0 (C-6),147.1(C-7),115.8(C-8),171.3 (C-9)。以上数据与文献[17]报道一致,因此确定化合物10 为咖啡酸(caffeic acid)。
化合物11 白色粉末 mp.271~273 ℃;分子式为 C9H6O4;EI-MSm/z178 [M]+;1H NMR(CH3OH,600 MHz)δ:6.20 (1H,d,J=9.5 Hz,H-3),7.80 (1H,d,J=9.5 Hz,H-4),6.75 (1H,s,H-5),6.94 (1H,s,H-8);13C NMR (CH3OD,151 MHz)δ:164.5 (C-2),112.6 (C-3),146.3 (C-4),113.1(C-5),144.7 (C-6),152.1 (C-7),103.7 (C-8),150.6 (C-9),112.9 (C-10)。以上数据与文献[18]报道一致,因此确定化合物11 为6,7-二羟基香豆素(aesculetin)。
化合物12 白色粉末 分子式为C23H46O2;EIMSm/z354 [M]+;1H NMR (CDCl3,400 MHz)δ:2.20 (1H,dd,J=18.4,15.3 Hz,H-2a),2.32(1H,dd,J=14.5,5.9 Hz,H-2b),0.81 (3H,d,J=6.3 Hz,3-CH3),0.93 (3H,d,J=6.6 Hz,7-CH3),0.85 (3H,t,J=6.6 Hz,19-CH3),3.89 (3H,s,-OCH3);13C NMR(CDCl3,100 MHz,)δ:180.1 (C-1),75.9 (C-2),34.1 (C-3),34.2 (C-4),27.4 (C-5),42.3 (C-6),38.4 (C-7),15.7 (C-8),20.9 (C-9),27.9 (C-10),30.8 (C-11),29.9 (C-12),29.8(C-13),29.8 (C-14),29.6 (C-15),29.5 (C-16),29.3 (C-17),32.1 (C-18),22.9 (C-19),13.9 (C-20)。以上数据与文献[19]报道一致,因此确定化合物12 为(3R)-3,6,7 三甲基十九碳酸甲酯[(3R)-methyl 3,6,7-trimethylnonadecanoate]。
化合物13 浅黄色针晶(氯仿) mp.265~270℃;分子式为C20H16N2O4;1H NMR (DMSO-d6,400 MHz)δ:5.27 (2H,s,H-5),8.68 (1H,s,H-7),8.11 (1H,d,J=8.1 Hz,H-9),7.70 (1H,t,J=7.6 Hz,H-10),7.85 (1H,t,J=7.5 Hz,H-11),8.16(1H,d,J=8.4 Hz,H-12),7.34 (1H,s,H-14),5.42(2H,s,H-17),0.88 (3H,t,J=7.0 Hz,H-18),1.86(2H,m,H-19);13C NMR (DMSO-d6,126 MHz)δ:152.7 (C-2),145.7 (C-3),50.5 (C-5),129.9 (C-6),131.9 (C-7),128.2 (C-8),128.8 (C-9),128.0(C-10),130.8 (C-11),129.2 (C-12),148.1 (C-13),97.2 (C-14),150.4 (C-15),157.2 (C-16a),119.3 (C-16),65.5 (C-17),8.0 (C-18),30.6 (C-19),72.7 (C-20),172.8 (C-21)。以上数据与文献[20]报道一致,因此确定化合物13 为喜树碱(camptothecin)。
化合物14 浅黄色针晶(氯仿) mp.255~260℃;分子式为C21H18N2O5;1H NMR (DMSO-d6,400 MHz)δ:4.03 (3H,s,-OCH3),5.24 (2H,s,H-5),8.84 (1H,s,H-7),7.15 (1H,d,J=7.6 Hz,H-10),7.76 (1H,m,H-11),7.71 (1H,d,J=8.5 Hz,H-12),7.31 (1H,s,H-14),5.42 (2H,s,H-17),0.87(3H,t,J=7.3 Hz,H-18),1.86 (2H,m,H-19),6.54(1H,s,-OH);13C NMR (DMSO-d6,125 MHz)δ:56.1 (C-OCH3),152.6 (C-2),145.5 (C-3),50.4(C-5),129.1 (C-6),126.0 (C-7),120.1 (C-8),154.9 (C-9),105.9 (C-10),130.6 (C-11),121.0(C-12),148.8 (C-13),96.7 (C-14),149.9 (C-15),156.8 (C-16a),119.0 (C-16),65.3 (C-17),7.7 (C-18),30.4 (C-19),72.3 (C-20),172.4 (C-21)。以上数据与文献报道[21]一致,因此确定化合物14 为9-甲氧基喜树碱(9-methoxycamptothecin)。
化合物15 浅黄色粉末 mp.230~237 ℃;分子式为C20H16N2O5;1H NMR (DMSO-d6,400 MHz)δ:5.21 (2H,s,H-5),8.43 (1H,s,H-7),7.26 (s,1H,H-9),7.40 (1H,d,J=9.0 Hz,H-11),8.00 (1H,d,J=9.1 Hz,H-12),7.24 (1H,s,H-14),5.39 (2H,s,H-17),0.86 (3H,t,J=7.1 Hz,H-18),1.84 (2H,m,H-19);13C NMR (DMSO-d6,100 MHz)δ:149.5(C-2),145.9 (C-3),50.2 (C-5),130.0 (C-6),129.4 (C-7),129.8 (C-8),108.9 (C-9),156.7 (C-10),123.1 (C-11),130.7 (C-12),143.3 (C-13),95.9 (C-14),150.2 (C-15),156.9 (C-16a),118.2(C-16),65.3 (C-17),7.9 (C-18),30.3 (C-19),72.5 (C-20),172.7 (C-21)。以上数据与文献[22]报道一致,因此确定化合物15 为10-羟基喜树碱(10-hydroxycamptothecin)。
化合物16 黄色粉末 mp.291~292 ℃;分子式为C17H14O7;1H NMR (DMSO-d6,500 MHz)δ:3.87(6H,s,CH3O-3',5'),6.19 (1H,d,J=1.9 Hz,H-6),6.55 (1H,d,J=1.9 Hz,H-8),6.98 (s,1H,H-3),7.32 (s,2H,H-2',6');13C NMR (DMSO-d6,126 MHz)δ:163.7 (C-2),103.6 (C-3),181.8 (C-4),157.4 (C-5),98.9 (C-6),164.2 (C-7),94.2 (C-8),161.4 (C-9),103.7 (C-10),56.4 (3',5'-OMe),120.4 (C-1'),104.4 (C-2',6'),148.2 (C-3',5'),139.9 (C-4')。以上数据与文献[23]报道的基本一致,因此确定化合物16 为麦黄酮(tricin)。
化合物17 白色粉末 mp.219~220 ℃;分子式为C29H50O2;EI~MSm/z429 [M]+。1H NMR(CH3OD,400 MHz)δ:3.59 (1H,m,H-3),5.60(1H,d,J=4.8 Hz,H-6),3.85 (1H,brs,H-7),0.68(3H,s,H-18),0.97 (3H,s,H-19),0.93 (3H,t,J=6.4 Hz,H-21),0.83 (3H,d,J=8.0 Hz,H-26),0.80(3H,d,J=8.0 Hz,H-27),0.88(3H,t,J=6.8 Hz,H-29);13C NMR (CH3OD,100 MHz)δ:37.6 (C-1),31.6 (C-2),71.6 (C-3),42.2 (C-4),146.5 (C-5),124.1 (C-6),65.6 (C-7),37.7 (C-8),42.5(C-9),37.2 (C-10),20.9 (C-11),39.4 (C-12),42.3 (C-13),49.6 (C-14),26.1 (C-15),28.5 (C-16),55.9 (C-17),11.8(C-18),18.5(C-19),36.3(C-20),18.9 (C-21),33.9 (C-22),29.9 (C-23),46.0 (C-24),24.5 (C-25),19.2 (C-26),20.0 (C-27),23.2 (C-28),12.2 (C-29)。以上数据与文献[11]报道一致,因此确定化合物17 为豆甾-5-烯-3β,7α-二醇(stigmast-5-en-3β,7α-diol)。
化合物18 白色粉末(氯仿) mp.283~284℃,分子式为C35H60O6,其1H NMR 和13C NMR 图谱与β-胡萝卜苷的标准图谱完全一致,TLC 上的斑点位置及显色与β-胡萝卜苷标准品的相同,且与标准品混合熔点不下降,所以确定化合物18 为β-胡萝卜苷(daucosterol)。
化合物19 白色针状结晶 mp.139~140 ℃,分子式为C29H50O,EI-MSm/z414[M]+,其1H NMR和13C NMR 图谱与β-谷甾醇的标准图谱完全一致,TLC 上的斑点位置及显色与β-谷甾醇标准品的相同,且与标准品混合熔点不下降,因此确定化合物19 为β-谷甾醇(sitosterol)。
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