石菖蒲的化学成分研究

2011-03-17 02:49仝晓刚程永现
天然产物研究与开发 2011年3期
关键词:无定形分子式柱层析

仝晓刚,程永现

1中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室,昆明650204; 2中国科学院研究生院,北京100049

石菖蒲的化学成分研究

仝晓刚1,2,程永现1*

1中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室,昆明650204;2中国科学院研究生院,北京100049

运用色谱法从石菖蒲根茎提取物中分离得到18个化合物,经波谱学分析鉴定为:(7S,8R)-4,9'-dihydroxyl-3,3'-dimethoxyl-7,8-dihydrobenzofuran-1'-propylneolignan(1),(7S,8R)-4,9'-dihydroxyl-3,3'-dimethoxyl-7,8-dihydrobenzofuran-1'-propylneoligan-9-O-β-D-glucopyranoside(2),7'-hydroxylariciresinol-9-acetate(3),5-羟基-3,7,4'-三甲氧基黄酮(4),野漆树苷(5),紫云英苷(6),松属素-3-O-芸香糖苷(7),山奈酚-3-O-芸香糖苷(8),德钦红景天苷(9),isoschaftoside(10),5-羟甲基糠醛(11),反式桂皮酸(12),3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oicacid(13),3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oic acid methyl ester(14),环阿屯醇(15),胡萝卜苷(16),羽扇豆醇(17),(22E,24R)-ergosta-5,7,22-trien-3β-ol(18)。除化合物4、11和16外,其余15个化合物均为首次从该植物中分离得到。

石菖蒲;天南星科;酚性成分;三萜

石菖蒲(Acorus tatarinowii Schott.)系天南星科(Araceae)菖蒲属多年生草本植物,其根茎为传统中药,主产四川、浙江、江苏等地,四川产者为道地药材。石菖蒲《神农本草经》列为上品,味辛性温,具芳香之气,行散之力强,为宣气通窍之佳品。中医学认为石菖蒲的功能主要是开窍豁痰、醒神益智、聪耳明目、化湿开胃和散寒除痹。临床广泛用于癫痫、痰厥、热病神昏、健忘、老年痴呆等疑难病的治疗[1]。菖蒲属植物主要含倍半萜[2],苯丙素[3]和糖[4]等成分[5,6],在我们对石菖蒲的系统研究中,曾经报道了从中分离得到的具有抗氧化作用的结构新颖的螺环生物碱、倍半萜、细辛醚类以及吡嗪类生物碱[7-9]。本文对其它酚性成分及三萜等18个化合物进行报道,其中15个系首次从该种中分离得到。

1 仪器与材料

核磁共振波谱仪为Brucker AM-400 MHz和 DRX-500 MHz,以TMS为内标。薄层层析硅胶和柱层析硅胶均为中国青岛海洋化工集团公司生产;反相硅胶RP-18为日产Daiso公司产品,Sephadex LH-20为法玛西雅公司生产。所用试剂如石油醚、氯仿、乙酸乙酯、丙酮、甲醇等均为化学纯试剂,用前重蒸。

石菖蒲根茎于2007年7月购自云南省药材公司,经云南省药材公司孙宏彦高级工程师鉴定为天南星科菖蒲属植物石菖蒲(A.tatarinowii Schott.),凭证标本(CHYX0001)存放于中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室。

2 提取与分离

该药材50 kg粉碎,水煎2次,每次2 h,残渣用95%乙醇提取2 h,减压浓缩干燥得粗提物4.7 kg,混悬于适量水中,75%乙醇醇沉,上清液减压浓缩至适量无醇味水液,依次用乙酸乙酯、正丁醇萃取3次,每次6 L。后经减压浓缩得乙酸乙酯萃取部分278 g,正丁醇萃取部分315 g和水部分2.3 kg。

乙酸乙酯部分(278 g)经硅胶柱层析,用氯仿-甲醇体系梯度洗脱(99∶1~70∶30)得5个部分(Fr.1~Fr.5)。Fr.3(52 g)经硅胶柱层析和Sephadex LH-20凝胶柱得化合物1(5 mg)和12(31 mg);Fr.4 (28 g)经硅胶柱层析,Sephadex LH-20凝胶柱和制备薄层纯化得化合物5(10 mg)和15(5 mg);Fr.5 (47 g)经多次硅胶柱层析和Sephadex LH-20凝胶柱得化合物13(5 mg)和14(4 mg)。

正丁醇部分(315 g)经硅胶柱层析,用氯仿-甲醇-水体系梯度洗脱(90∶10∶0~70∶30∶5)得4个部分(Fr.1~Fr.4)。Fr.1(32 g)经硅胶柱和RP-18柱反复柱层析,再经Sephadex LH-20凝胶柱纯化得化合物2(6 mg),4(5 mg)和16(7 mg);Fr.2(63 g)经硅胶柱和RP-18柱反复柱层析,再经Sephadex LH-20凝胶柱和重结晶得化合物6(5 mg),8(4 mg),11 (4 mg),17(7 mg)和18(5 mg);Fr.3(55 g)经硅胶柱和Sephadex LH-20凝胶柱反复柱层析,再经RP-18柱得化合物3(4 mg),7(12 mg)和10(3 mg);Fr.4(72 g)经硅胶柱层析和Sephadex LH-20凝胶柱得化合物9(7 mg)。

3 结构鉴定

化合物1 淡黄色油状物,分子式为C20H24O6;1H NMR(500 MHz,CD3OD):δH6.89(1H,d,J= 1.7 Hz,H-2),6.94(1H,dd,J=8.3 Hz,1.7 Hz,H-6),6.91(1H,d,J=8.3 Hz,H-5),6.73,6.72(2× 1H,2×br s,H-2',H-6'),5.53(1H,d,J=5.9 Hz,H-7),3.84(1H,m,Ha-9),3.81,3.79(2×3H,2×s,3-OCH3,3'-OCH3),3.70(1H,m,Hb-9),3.57(2H,t,J =6.5 Hz,H-9'),3.46(1H,m,H-8),2.63(2H,t,J =7.7 Hz,H-7'),1.82(2H,m,J=6.5 Hz,H-8');13C NMR(125 MHz,CD3OD):δC134.8(C-1),110.6(C-2),149.1(C-3),147.5(C-4),114.1(C-5),119.7 (C-6),89.0(C-7),55.4(C-8),65.0(C-9),136.9 (C-1'),116.1(C-2'),136.9(C-3'),145.2(C-4'),129.9(C-5'),117.9(C-6'),32.9(C-7'),35.7(C-8'),62.2(C-9'),56.4(3-OCH3),56.8(3'-OCH3)。其波谱数据与文献[10]报道基本一致,故鉴定化合物1为(7S,8R)-4,9'-dihydroxyl-3,3'-dimethoxyl-7,8-dihydrobenzofuran-1'-propylneolignan.

化合物2 淡黄色油状物,分子式为C26H34O11;1H NMR(400 MHz,CD3OD):δH6.99(1H,d,J= 1.5 Hz,H-2),6.79(1H,dd,J=8.0 Hz,1.5 Hz,H-6),6.66(1H,d,J=8.0 Hz,H-5),6.58(1H,2×br s,H-6'),6.49(1H,2×br s,H-2'),5.41(1H,d,J= 6.4 Hz,H-7),3.94(1H,m,Ha-9),3.81,3.80(2× 3H,2×s,3-OCH3,3'-OCH3),3.73(1H,m,Hb-9),3.41(2H,t,J=6.8 Hz,H-9'),3.48(1H,m,H-8),2.43(2H,t,J=8.0 Hz,H-7'),1.82(2H,m H-8'),4.35(1H,d,J=7.8 Hz,Glc H-1),3.22~3.87(6H,m,Glc H-2~H-6);13C NMR(100 MHz,CD3OD):δC134.6(C-1),110.6(C-2),148.9(C-3),147.4(C-4),114.0(C-5),119.7(C-6),89.0(C-7),52.8(C-8),71.6(C-9),136.9(C-1'),116.0(C-2'),137.0 (C-3'),145.2(C-4'),129.6(C-5'),118.2(C-6'),32.9(C-7'),35.8(C-8'),62.2(C-9'),56.4(3-OCH3),56.7(3'-OCH3),104.2(Glc-1),75.1(Glc-2),78.0(Glc-3),71.6(Glc-4),78.2(Glc-5),62.7 (Glc-6)。其波谱数据与文献[10]报道一致,故鉴定化合物2为(7S,8R)-4,9'-dihydroxyl-3,3'-dimethoxyl-7,8-dihydrobenzofuran-1'-propylneoligan-9-O-β-D-glucopyranoside。

化合物3 黄色油状物,分子式为C22H26O8;1H NMR(400 MHz,CD3OD):δH6.96(1H,d,J=1.5 Hz,H-2),6.90(1H,d,J=8.2 Hz,H-5),6.87(1H,dd,J=8.2 Hz,1.5 Hz,H-6),6.94(1H,d,J=1.5 Hz,H-2'),6.92(1H,d,J=8.2 Hz,H-5'),6.88(1H,dd,J=8.2 Hz,1.5 Hz,H-6'),4.54(1H,d,J=5.9 Hz,H-7),2.51(1H,m,H-8),4.51(1H,m,Ha-9),4.54(1H,m,Hb-9),3.83(3H,s,3-OCH3),4.28 (1H,d,J=5.5 Hz,H-7'),2.13(1H,m,H-8'),3.92 (1H,m,Ha-9'),3.97(1H,m,Hb-9'),3.81(3H,s,3'-OCH3),1.81(3H,s,O=CCH3);13C NMR(100 MHz,CD3OD):δC135.3(C-1),111.3(C-2),150.5 (C-3),150.0(C-4),112.6(C-5),120.3(C-6),85.7 (C-7),50.3(C-8),64.9(C-9),137.3(C-1'),111.4 (C-2'),150.5(C-3'),150.2(C-4'),112.7(C-5'),120.5(C-6'),76.3(C-7'),51.2(C-8'),71.3(C-9'),56.4(3-OCH3),56.5(3'-OCH3),172.5(C= O),20.6(O=CCH3)。其波谱数据与文献[11]报道一致,故鉴定化合物3为7'-hydroxylariciresinol-9-acetate。

化合物4 黄色无定形粉末,分子式为C18H16O6;1H NMR(500 MHz,CDCl3):δH6.35(1H,d,J= 2.2 Hz,H-6),6.44(1H,d,J=2.2 Hz,H-8),8.08 (2H,d,J=8.9 Hz,H-2'和H-6'),7.02(2H,d,J= 8.9 Hz,H-3'和H-5'),12.7(1H,s,OH-5);13C NMR (125 MHz,CDCl3):δC155.9(C-2),138.8(C-3),178.8(C-4),156.7(C-5),97.8(C-6),165.4(C-7),92.1(C-8),162.0(C-9),106.5(C-10),122.8(C-1'),130.1(C-2'),114.0(C-3'),161.7(C-4'),114.0(C-5'),130.1(C-6'),55.4,55.4,55.8(3× OCH3)。其波谱数据与文献[12]报道基本一致,故鉴定化合物4为5-hydroxy-3,7,4'-trimethoxyflavone。

化合物5 黄色无定形粉末,分子式为C27H30O14;1H NMR(500 MHz,CD3OD):δH6.35(1H,s,H-3),6.29(1H,d,J=2.0 Hz,H-6),6.74(1H,d,J= 2.0 Hz,H-8),7.59(2H,d,J=8.6 Hz,H-2'和H-6'),6.65(2H,d,J=8.6 Hz,H-3'和H-5'),13.80 (1H,s,OH-5),8.09(1H,s,OH-4'),5.38(1H,d,J =7.2 Hz,Glc H-1),5.09(1H,d,J=6.1 Hz,Rha H-1),3.10~3.96(10H,m,Glc H-2~H-6和Rha H-2–H-5),1.20(3H,d,J=6.4 Hz,Rha H-6);13C NMR(125 MHz,CD3OD):δC161.2(C-2),102.3(C-3),182.2(C-4),159.6(C-5),98.1(C-6),164.0(C-7),92.9(C-8),163.4(C-9),102.9(C-10),121.4 (C-1'),129.3(C-2'),116.1(C-3'),157.7(C-4'),116.1(C-5'),129.3(d,C-6'),107.3(Glc-1),81.5 (Glc-2),75.1(Glc-3),60.9(Glc-4),84.8(Glc-5), 70.9(Glc-6),110.1(Rha-1),74.6(Rha-2),70.9 (Rha-3),73.4(Rha-4),74.6(Rha-5),17.1(Rha-6)。其波谱数据与文献[13]报道基本一致,故鉴定化合物5为rhoifolin。

化合物6 黄色无定形粉末,分子式为C21H20O11;1H NMR(400 MHz,CD3OD):δH6.19(1H,d,J= 1.9 Hz,H-6),6.42(1H,d,J=1.9 Hz,H-8),8.03 (2H,d,J=8.8 Hz,H-2'和H-6'),6.87(2H,d,J= 8.8 Hz,H-3'和H-5'),12.62(1H,s,OH-5),5.45 (1H,d,J=7.3 Hz,Glc H-1),3.07~3.56(6H,m,Glc H-2–H-6);13C NMR(100 MHz,CD3OD):δC156.3(C-2),133.2(C-3),177.5(C-4),161.2(C-5),98.8(C-6),164.4(C-7),93.5(C-8),160.0(C-9),104.0(C-10),120.9(C-1'),130.9(C-2'),115.1 (C-3'),156.4(C-4'),115.1(C-5'),130.9(d,C-6'),100.8(Glc-1),74.2(Glc-2),76.4(Glc-3),69.9 (Glc-4),77.5(Glc-5),60.8(Glc-6)。其波谱数据与文献[14]报道基本一致,故鉴定化合物6为astragalin。

化合物7 黄色油状物,分子式为 C27H32O13;1H NMR(400 MHz,CD3OD):δH5.34(1H,dd,J =13.1,2.9 Hz,H-2),6.15(1H,s,H-6),6.22(1H,s,H-8),8.05(1H,t,J=7.8 Hz,H-4'),7.52(2H,d,J=7.8 Hz,H-2'和H-6'),7.42(2H,t,J=7.8 Hz,H-3'和H-5'),12.43(1H,s,OH-5),5.32(1H,d,J= 7.6 Hz,Glc H-1),5.12(1H,d,J=5.2 Hz,Rha H-1),3.08~3.64(12H,m,H-3a,H-3b,Glc H-2~H-6,Rha H-2~H-5),0.96(3H,d,J=6.0 Hz,Rha H-6);13C NMR(100 MHz,CD3OD):δC81.9(C-2),41.2(C-3),196.9(C-4),101.4(C-5),99.0(C-6),165.2(C-7),94.0(C-8),162.5(C-9),104.2(C-10),138.5(C-1'),130.4(C-2'),128.7(C-3'),130.9(C-4'),128.7(C-5'),130.4(d,C-6'),100.6 (Glc-1),74.1(Glc-2),75.7(Glc-3),70.0(Glc-4),76.3(Glc-5),68.4(Glc-6),100.9(Rha-1),70.6 (Rha-2),69.2(Rha-3),70.4(Rha-4),71.8(Rha-5),17.9(Rha-6)。其波谱数据与文献[15]报道一致,故鉴定化合物7为pinocembrin-7-O-rutinoside。

化合物8 黄色无定形粉末,分子式为C27H30O15;1H NMR(400 MHz,CD3OD):δH6.19(1H,d,J= 0.9 Hz,H-6),6.39(1H,d,J=0.9 Hz,H-8),7.97 (2H,d,J=8.6 Hz,H-2'和H-6'),6.87(2H,d,J= 8.6 Hz,H-3'和H-5'),12.56(1H,s,OH-5),5.29 (1H,d,J=7.4 Hz,Glc H-1),5.11(1H,d,J=4.8 Hz,Rha H-1),3.04~3.68(10H,m,Glc H-2~H-6和Rha H-2~H-5),0.96(3H,d,J=6.1 Hz,Rha H-6);13C NMR(100 MHz,CD3OD):δC156.5(C-2),133.2(C-3),177.4(C-4),161.2(C-5),98.8(C-6),164.2(C-7),93.8(C-8),159.9(C-9),104.0(C-10),120.9(C-1'),130.9(C-2'),115.1(C-3'),156.9(C-4'),115.1(C-5'),130.9(C-6'),100.8 (Glc-1),74.2(Glc-2),75.7(Glc-3),69.9(Glc-4),76.3(Glc-5),66.9(Glc-6),101.3(Rha-1),70.6 (Rha-2),68.3(Rha-3),70.3(Rha-4),71.8(Rha-5),17.8(Rha-6)。其波谱数据与文献[16]报道基本一致,故鉴定化合物8为kaempferol-3-O-rutinoside。

化合物9 黄色无定形粉末,分子式为C21H20O11;1H NMR(400 MHz,CD3OD):δH6.56(1H,s,H-6),7.89(2H,d,J=8.2 Hz,H-2'和 H-6'),6.89 (2H,d,J=8.2 Hz,H-3'和H-5'),5.65(1H,d,J= 1.8 Hz,Rha H-1),3.32~3.91(4H,m,Rha H-2~H-5),1.26(3H,d,J=6.1 Hz,Rha H-6);13C NMR(100 MHz,CD3OD):δC151.6(C-2),135.8(C-3),176.4 (C-4),144.5(C-5),98.3(C-6),150.1(C-7),127.6 (C-8),147.4(C-9),104.6(C-10),121.8(C-1'),129.1(C-2'),115.4(C-3'),159.4(C-4'),115.4(C-5'),129.1(C-6'),99.6(Rha-1),69.9(Rha-2),70.1 (Rha-3),71.7(Rha-4),69.9(Rha-5),17.9(Rha-6)。其波谱数据与文献[17]报道基本一致,故鉴定化合物9为rhodionin。

化合物10 黄色无定形粉末,分子式为C26H28O14;1H NMR(500 MHz,CD3OD):δH6.62(1H,s,H-3),7.98(2H,d,J=8.3 Hz,H-2'和 H-6'),6.93 (2H,d,J=8.3 Hz,H-3'和H-5'),4.97(1H,d,J= 7.1 Hz,Glc H-1),4.87(1H,d,J=4.9 Hz,Ara H-1),3.54~3.81(11H,m,Glc H-2~H-6和Ara H 2~H-5);13C NMR(125 MHz,CD3OD):δC166.7(C-2),103.9(C-3),184.3(C-4),162.8(C-5),108.5(C-6),158.9(C-7),105.8(C-8),156.8(C-9),105.1 (C-10),123.4(C-1'),130.3(C-2'),117.2(C-3'),162.9(C-4'),117.2(C-5'),130.3(d,C-6'),75.0 (Glc-1),72.4(Glc-2),80.3(Glc-3),70.4(Glc-4),83.0(Glc-5),63.1(Glc-6),76.5(Ara-1),75.2(Ara-2),73.2(Ara-3),71.3(Ara-4),71.9(Ara-5)。其波谱数据与文献[18]报道一致,故鉴定化合物10为isoschaftoside。

化合物11 淡黄色油状物,分子式为C6H6O3;1H NMR(500 MHz,CD3OD):δH4.61(2H,s,5-CH2OH),6.58(1H,d,J=3.5 Hz,H-4),7.38 (1H,d,J=3.5 Hz,H-3),9.53(1H,s,2-CHO);13C NMR(125 MHz,CD3OD):δC153.9(C-2),124.9(C-3),110.9(C-4),163.2(C-5),179.4(2-CHO),57.6 (5-CH2OH)。其波谱数据与文献[19]报道一致,故鉴定化合物11为5-hydroxymethyl-2-furaldehyde。

化合物12 淡黄色油状物,分子式为C9H8O2;1H NMR(400 MHz,CD3OD):δH6.53(1H,d,J=16.0 Hz,H-8),7.40(1H,t,J=8.5 Hz,H-4),7.41(2H,m,H-3和H-5),7.57(1H,d,J=16.0 Hz,H-7),7.67(2H,dd,J=8.5 Hz,2.5Hz,H-2和H-6);13C NMR(100 MHz,CD3OD):δC134.3(C-1),128.2(C-2),128.9(C-3),130.2(C-4),128.9(C-5),128.2(C-6),143.7(C-7),119.6(C-8),167.3 (C-9)。其波谱数据与文献[20]报道一致,故鉴定化合物12为trans-cinnamic acid。

化合物13 白色无定形粉末,分子式为C30H42O6;1H NMR(400 MHz,CDCl3):δH5.85(1H,s,H-16),4.81(1H,t,J=8.8 Hz,t,H-7),3.22(1H,m,H-3),1.67(3H,s,H-30),1.26(3H,s,H-18),1.25 (3H,s,H-19),1.27(3H,d,J=6.1 Hz,H-27),1.03 (3H,m,H-21),1.04(3H,s,H-28),0.86(3H,s,H-29);13C NMR(100 MHz,CDCl3):δC34.3(C-1),27.5(C-2),78.2(C-3),38.6(C-4),49.3(C-5),26.5(C-6),66.6(C-7),158.1(C-8),142.4(C-9),38.9(C-10),191.9(C-11),44.4(C-12),51.5(C-13),58.3(C-14),209.5(C-15),122.4(C-16),186.8(C-17),39.6(C-18),18.6(C-19),28.2(C-20),20.8(C-21),49.3(C-22),205.9(C-23),46.4 (C-24),34.3(C-25),170.4(C-26),16.9(C-27),28.2(C-28),15.5(C-29),33.1(C-30)。其波谱数据与文献[21]报道一致,故鉴定化合物13为3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oicacid。

化合物14 白色无定形粉末,分子式为C31H44O7;1H NMR(500 MHz,CDCl3):δH5.86(1H,s,H-16),4.79(1H,m,H-7),3.67(3H,s,OCH3),3.16 (1H,m,H-3),1.48(3H,s,H-30),1.17(3H,s,H-18),1.15(3H,s,H-19),1.13(3H,d,J=6.9 Hz,H-27),1.06(3H,d,J=7.0 Hz,H-21),0.99(3H,s,H-28),079(3H,s,H-29);13C NMR(125 MHz,CDCl3): δC34.6(C-1),27.8(C-2),78.3(C-3),38.7(C-4), 49.4(C-5),26.2(C-6),67.1(C-7),158.1(C-8),142.2(C-9),38.7(C-10),197.3(C-11),44.4(C-12),51.5(C-13),58.3(C-14),210.8(C-15),122.4 (C-16),187.5(C-17),30.9(C-18),18.5(C-19),28.6(C-20),19.5(C-21),49.4(C-22),205.9(C-23),46.4(C-24),34.8(C-25),176.0(C-26),17.1 (C-27),28.2(C-28),15.5(C-29),33.2(C-30),51.9(OCH3)。其波谱数据与文献[21]报道基本一致,故鉴定化合物14为3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oic acid methyl ester。

化合物15 白色无定形粉末,分子式为C30H50O;1H NMR(500 MHz,CDCl3):δH5.10(1H,t,J= 6.8 Hz,H-24),3.28(1H,m,H-3),1.60(3H,s,H-26),1.68(3H,s,H-27),0.97(3H,s,H-18),0.96 (3H,s,H-28),0.89(3H,s,H-21),0.88(3H,d,J= 7.0 Hz,H-30),0.81(3H,br s,H-29);13C NMR(125 MHz,CDCl3):δC31.9(C-1),30.4(C-2),78.9(C-3),40.5(C-4),47.1(C-5),21.2(C-6),25.9(C-7),48.0(C-8),20.0(C-9),26.0(C-10),26.5(C-11),32.9(C-12),45.3(C-13),48.8(C-14),35.6(C-15),28.1(C-16),52.3(C-17),17.0(C-18),29.9 (C-19),35.9(C-20),18.2(C-21),36.3(C-22),24.9(C-23),114.3(C-24),148.3(C-25),15.2(C-26),22.9(C-27),22.0(C-28),14.0(C-29),17.0 (C-30)。其波谱数据与文献[22]报道基本一致,故鉴定化合物15为cycloartenol。

化合物16 白色无定形粉末,分子式为C35H60O6;1H NMR(500 MHz,CD3OD):δH0.67(3H,s,H-18),0.82(3H,m,H-27),0.84(3H,m,H-29),0.91 (3H,m,H-26),0.93(3H,s,H-19),0.97(3H,m,H-21),1.38(1H,m,H-14),3.66(1H,m,H-3),5.34 (1H,m,H-6),4.91(1H,d,J=5.2 Hz,Glc H-1),3.14~3.54(6H,m,Glc H-2~H-6);13C NMR(125 MHz,CD3OD):δC37.6(C-1),30.0(C-2),77.5(C-3),39.0(C-4),140.5(C-5),121.3(C-6),32.1(C-7),32.1(C-8),50.3(C-9),36.9(C-10),21.3(C-11),39.7(C-12),42.6(C-13),56.9(C-14),24.6 (C-15),28.5(C-16),56.1(C-17),12.4(C-18),19.7(C-19),36.2(C-20),19.3(C-21),34.1(C-22),26.1(C-23),45.9(C-24),29.4(C-25),19.8 (C-26),20.4(C-27),23.3(C-28),12.5(C-29),100.9(Glc-1),74.2(Glc-2),77.6(Glc-3),70.8 (Glc-4),77.5(Glc-5),61.8(Glc-6)。其波谱数据与文献[23]报道基本一致,故鉴定化合物16为daucosterol。

化合物17 白色无定形粉末,分子式为C30H50O;1H NMR(500 MHz,CDCl3):δH4.68(1H,br s,Ha-29),4.57(1H,br s,Hb-29),3.19(1H,dd,J=5.0,5.0 Hz,H-3),0.76,0.78,0.82,0.94,0.98,1.03,1.38(each 3H,s,H-23,24,25,26,27,28,29);13C NMR(125 MHz,CDCl3):δC38.7(C-1),27.4(C-2),78.9(C-3),38.8(C-4),55.3(C-5),18.3(C-6),34.2(C-7),40.8(C-8),50.4(C-9),37.1(C-10),20.9(C-11),25.1(C-12),38.0(C-13),42.9(C-14),27.4(C-15),35.5(C-16),42.8(C-17),48.3 (C-18),47.9(C-19),151.0(C-20),29.8(C-21),40.0(C-22),27.9(C-23),15.4(C-24),16.1(C-25),15.9(C-26),14.5(C-27),18.0(C-28),109.3 (C-29),19.3(C-30)。其波谱数据与文献[24]报道基本一致,故鉴定化合物17为lupeol。

化合物18 白色无定形粉末,分子式为C28H44O;1H NMR(500 MHz,CDCl3):δH5.60(1H,br s,H-6),5.42(1H,br s,H-7),5.24(2H,br s,H-22和H-23),3.67(1H,br s,H-3),1.08(3H,br s,H-24),0.98(3H,s,H-19),0.96(3H,br s,H-21),0.87 (6H,br s,H-26和H-27),0.67(3H,s,H-18);13C NMR(125 MHz,CDCl3):δC39.0(C-1),32.0(C-2),71.1(C-3),40.8(C-4),139.8(C-5),119.6(C-6),116.3(C-7),141.4(C-8),49.4(C-9),37.9(C-10),22.1(C-11),40.2(C-12),42.8(C-13),54.5(C-14),23.0(C-15),28.2(C-16),55.7(C-17),12.0 (C-18),16.3(C-19),40.4(C-20),21.1(C-21),135.7(C-22),131.9(C-23),42.8(C-24),33.0(C-25),17.6(C-26),19.6(C-27),19.9(C-28)。其波谱数据与文献[25]报道基本一致,故鉴定化合物18为(22E,24R)-ergosta-5,7,22-trien-3β-ol。

1 Wu QD(吴启端),Wu Q(吴清).Research advancement for the pharmacology of Acorus tatarinowii.Tradit Chin Drug Res Clin Pharm(中药新药与临床药理),2006,17:477-480.

2 Nawamaki K,Kuroyanagi M.Sesquiterpenoids from Acorus calamus as germination inhibitors.Phytochemistry,1996,43: 1175-1182.

3 Saxena DB.Phenyl indane from Acorus calamus.Phytochemistry,1986,25:553-555.

4 Tao H(陶宏),Zhu EY(朱恩圆),Wang ZT(王峥涛).Chemical study on the rhizome of Acorus tatarinowii.Chin J Nat Med(中国天然药物),2006,14:159-160.

5Hong YF(洪永福),Guo XM(郭学敏),Sun LN(孙连娜),et al.Isolation and identification of the polysaccharide of Acorus gramincus Soland.J Pharm Pract(药学实践杂志),1998,16:149-151.

6 Liu CH(刘春海),Liu XJ(刘西京),Yang HS(杨华生).GC-MS analysis of essential oils from Acorus tatarinowwi Schott.Chin Arch Tradit Chin Med(中医药学刊),2006,24: 1280-1281.

7 Tong XG,Zhou LL,Wang YH,et al.Acortatarins A and B,two novel antioxidative spiroalkaloids with a naturally unusual morpholine motif from Acorus tatarinowii.Org Lett,2010,12:1844-1847.

8 Tong XG,Wu GS,Huang CG,et al.Compounds from Acorus tatarinowii:Determination of absolute configuration by quantum computations and cAMP regulation activity.J Nat Prod,2010,73:1160-1163.

9 Tong XG,Qiu B,Luo GF,et al.Alkaloids and sesquiterpenoids from Acorus tatarinowii.J Asian Nat Prod Res,2010,12:438-442.

10 Feng WS(冯卫生),Zheng XK(郑晓珂),Wang YZ(王彦志),et al.Isolation and structure indentification of the chemical constituents from pine needles of Pinus massoniana Lama.Nat Prod Res Dev(天然产物研究与开发),2004,16: 500-502.

11 Shuichi Y,Angelika O,Bernd RT.Lignans in resin of Araucaria angustifolia by gas chromatography mass spectrometry.J Mass Spectrum,2004,39:1337-1347.

12 Dong H,Gou YL,Cao SG,et al.Eicosenones and methylated flavonols from Amomum koenigii.Phytochemistry,1999,50: 899-902.

13 He ZD(贺震旦),Liu YQ(刘玉青),Yang CR(杨崇仁).Glycosides from Ligustrum purpurascens.Acta Bot Yunnannica(云南植物研究),1992,14:328-336.

14 Wu T,Abdulla R,Yang Y,et al.Flavonoids from Gossypium hisutum flowers.Chem Nat Compd,2008,44:370-371.

15 Kapetanidis J,Kokkalow E.Flavonoids from the aerial parts of Ziziphora taurica marsch.Bieb.ssp.celeonioides(Bioss.) P.H.Davis(Lamiaceae).Pharm Acta Helv,1998,63:206-208.

16 Bhutani SP,Chibber SS,Seshadri TR.Flavonoids of the fruits and leaves of Tribulus terrestris.Phytochemistry,1969,8:299-303.

17 Zhou LY(周凌云),Zhang XH(张祥华),Chen CX(陈昌祥)Chemical study on Rhodiola from Lijiang.Nat Prod Res Dev(天然产物研究与开发),2004,16:410-414.

18 Gong YH(龚运淮),Ding LS(丁立生).Carbon-13 Nuclear Magnetic Resonance of Natural Organic Compound(天然产物核磁共振13C NMR碳谱分析).Yunnan,Yunan Technology Pubishing House,2005.546.

19 Qin WJ(秦文杰),Wang GL(王钢力),Lin RC(林瑞超).Studies on chemical constituents of Heterosmilax yunnanenis.Chin Tradit Herb Drugs(中草药).2007,30:959-961.

20 Ripperger H,Diaz M,Schreiber K.Two cinnamoyl derivatives from Cinnamomum triplinervis.Phytochemistry,1981,20: 1453-1454.

21 Guan SH,Yang M,Wang XM,et al.Spectral assignments and reference data structure elucidation and complete NMR spectral assignments of three new lanostanoid triterpenes with unprecedented 16,17 double bond from Ganoderma lucidum.Magn Reson Chem,2007,45:789-791.

22 He P(何萍),Li S(李帅),Wang SJ(王素娟),et al.Study on chemical constituents in rhizome of Pinellia ternate.China J Chin Mater Med(中国中药杂志),2005,30:671-674.

23 Sun HX(孙红祥),Ye YP(叶益萍),Yang K(杨可).Studies on the chemical constituents in Radix astilbes Chinensis.China J Chin Mater Med(中国中药杂志),2002,27:751-754.

24 Gao S(聕嵩),Fu GM(浮光苗),Fan LH(范丽华),et al.Studies on the chemical constituents from roots of Lysidice rhodostegia Hance.Chin J Nat Med(中国天然药物),2005,3:144-147.

25 Yan M(严敏),Tang HM(汤洪敏),Hu DY(胡德禹).Study on rite chemical constituent of Tricholoma giganteum Massee.J Anhui Agric Sci(安徽农业科学),2008,36: 14614-14616.

Chemical Constituents from Acorus tatarinowii

TONG Xiao-gang1,2,CHENG Yong-xian1*1State Key Laboratory of Phytochemistry and Plant Resources in West China,Kunming Institute of Botany,The Chinese Academy of Sciences,Kunming 650204,China;2Graduate School of the Chinese Academy of Sciences,Beijing 100049,China

Eighteen compounds were isolated from the rhizome of Acorus tatarinowii.Their structures were identified by spectroscopic data as(7S,8R)-4,9'-dihydroxyl-3,3'-dimethoxyl-7,8-dihydrobenzofuran-1'-propylneolignan(1),(7S,8R)-4,9'-dihydroxyl-3,3'-dimethoxyl-7,8-dihydrobenzofuran-1'-propylneoligan-9-O-β-D-glucopyranoside(2),7'-hydroxylariciresinol-9-acetate(3),5-hydroxy-3,7,4'-trimethoxyflavone(4),rhoifolin(5),astragalin(6),pinocembrin-7-O-rutinoside(7),kaempferol-3-O-rutinoside(8),rhodionin(9),isoschaftoside(10),5-hydroxymethyl-2-furaldehyde(11),trans-cinnamic acid(12),3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oicacid(13),3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oic acid methyl ester(14),cycloartenol(15),daucosterol(16),lupeol (17),(22E,24R)-ergosta-5,7,22-trien-3β-ol(18).Except for compounds 4,11,and 16,all the other substances were obtained from this plant for the first time.

Acorus tatarinowii;Araceae;phenols;triterpenoids

1001-6880(2011)03-0404-06

2010-08-23 接受日期:2010-12-09

中国科学院知识创新重要方向项目(KSCX2-YW-R-118和KSCX2-YW-R-211);中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室自主课题项目(P2008-ZZ11);云南省中青年学术技术带头人与后备人才项目(2007PY01-48);国家十一五科技部重大新药创制项目(2008ZX09401-004)

*通讯作者 Tel:86-871-5223048;E-mail:yxcheng@mail.kib.ac.cn

R284.2;R946

A

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