贵州鼠尾草化学成分的研究

王和英,胡德禹,薛 伟,杨 松,宋宝安

贵州大学精细化工研究开发中心教育部绿色农药与生物工程重点实验室,贵阳 550025

贵州鼠尾草化学成分的研究

王和英,胡德禹＊,薛 伟,杨 松,宋宝安

贵州大学精细化工研究开发中心教育部绿色农药与生物工程重点实验室,贵阳 550025

从贵州鼠尾草 95%乙醇提取物分离得到 8个化合物,通过理化性质及波谱方法分别鉴定为正三十三烷(1),十二烷酸十四烷酯 (2),β-谷甾醇 (3),胡萝卜苷 (4),乌苏酸 (5),2a,3β-二羟基乌苏酸 (6),白桦酸 (7)和迷迭香酸 (8)。以上化合物均首次从该植物中分离得到。

贵州鼠尾草;化学成分

Abstract:Eight compoundswere isolated form the 95%ethanol extract of the whole plants ofSalvia cavalerieiLévl.On the basis of physicochemical properties and spectral methods they were identified as tritriacontane(1),myristyl dodecanoate(2),β-sitosterol(3),daucosterol(4),ursolic acid(5),2a,3β-dihydroxyursolic acid(6),betulinic acid(7),ros marinic acid(8).All of the compoundswere isolated from the stems of this plant for the first time.

Key words:Salvia cavalerieiLévl;chemical constituents

鼠尾草为唇形科 (Labiatae)鼠尾草属 (Salvia)植物。鼠尾草属植物全球有 900种,占全科植物总数的 20%,宜生长于温热带地区[1]。我国鼠尾草植物品种,据《中国药物志》记载有 83种,25变种,9变型,其中药用 30余种 (含变种,变型),分布于全国各地[2]。贵州鼠尾草 (Salvia cavalerieiLévl)别名:朱砂草,血盆草,反背红,叶下红等,是贵州民间中草药,在民间是一味常用的中草药,治疗范围广,疗效确切。其主要作用有有凉血解毒,散瘀止血等功效。近年来,随着对鼠尾草属植物活性成分及药理作用研究[3-5]的深入,鼠尾草植物在临床的应用也有了广泛的发展。而到目前为止贵州鼠尾草化学成分国内还没有相关报道,因此我们对贵州鼠尾草化学成分进行了研究,从其全草 95%乙醇提取物中分离得到 8个化合物,所得化合物均首次从该植物中分离得到。

1 仪器和试剂

X-4型数字显微熔点测定仪 (温度未校正);日本电子 JOEL-ECX500型 500 MHz核磁共振仪 (T MS为内标);HPMS 5973质谱仪 (美国惠普公司)。柱色谱硅胶及薄层色谱硅胶均为青岛海洋化工出品;所用试剂均为分析纯。

贵州鼠尾草采自贵州省兴义市,经贵阳医学院药学院教研室主任龙庆德鉴定为唇形科鼠尾草属植物贵州鼠尾草 (Salvia cavalerieiLévl),标本保存于贵州大学精细化工研究开发中心。

2 提取分离

晒干的贵州鼠尾草全草 11 kg粉碎后,用 95%的乙醇加热回流提取三次,每次 2 h,合并提取液,减压浓缩至无醇味得稠浸膏 1258 g。加水使成混悬液,依次用石油醚,乙酸乙酯,正丁醇萃取,合并各萃取液并经减压浓缩,分别得石油醚萃取物 208 g,乙酸乙酯萃取物 171 g,正丁醇萃取物 106 g。萃取物经反复硅胶柱层析分离,分别用石油醚-乙酸乙酯系统 (1∶0～1∶1),氯仿 -甲醇系统 (1∶0～0∶1)进行梯度洗脱。经多次柱色谱分离,纯化和重结晶,最后分离得到 8个化合物,分别为正三十三烷 (65 mg),十二烷酸十四烷酯 (37 mg),β-谷甾醇 (102 mg),胡萝卜苷 (218 mg),乌苏酸 (550 mg),2a,3β-二羟基乌苏酸 (85 mg),白桦酸 (22 mg)和迷迭香酸 (28 mg)。

3 结构鉴定

化合物 1 白色固体 (氯仿),mp.68～70℃,在紫外,磷钼酸,碘缸中均不显色。分子式为 C33H68;E IMSm/z:464[M]+;IR(KBr)cm-1:2849,2916,1472,1462,729,719;1H NMR(CDCl3,500 MHz)δ:0.88(6H,t,J=6.9 Hz,2CH3),1.25(62 H,s,31CH2),13C NMR(CDCl3,125 MHz)δ:14.13(2C,1,1′-C),22.70(2C,2,2′-C),31.93(2C,3,3′-C),29.38-29.71(27C),上述光谱数据与文献[6]报导一致,可鉴定该化合物为正三十三烷。

化合物 2 白色固体 (氯仿),mp.60～64℃,在紫外,磷钼酸,碘缸中均显色。分子式为 C26H52O2;E IMSm/z:396[M]+;IR(KBr)cm-1:2955,2916,2849,1736(羰基),1472,1462,1173,729,719;1H NMR(CDCl3,500 MHz)δ:0.88(6H,t,H-1,26),2.29(2H,t,H-11),4.05(2H,t,H-13),1.61(2H,t,H-10),1.55(2H,t,H-14),1.25(38H,m,H-2 to 9,15 to 25);13C NMR(CDCl3,125MHz)δ:14.1(C-1,26),22.7(C-2,25),25.1(C-10),25.9(C-15),31.9(C-3,24),34.5(C-11),29.2-29.7(C-4 to 9,C-14,16 to 23),64.4(C-13),174.0(C-12),通过 I R,1H NMR,13C NMR与质谱可鉴定该化合物为十二烷酸十四烷酯。

化合物 3 白色针状固体 (氯仿),mp.132.2～132.9℃,在磷钼酸,碘缸中显色。分子式为 C29H50O;E IMSm/z:414[M]+;IR(KBr)cm-1:3426(羟基),2959,2866(饱和脂环氢),1458,1375(碳碳双键);1H NMR(CDCl3,500 MHz)δ:5.35(1H,H-7),3.52(1H,-OH);13C NMR(CDCl3,125 MHz)δ:140.8(C-5),121.8(C-7),71.9(C-1),56.8(C-17),56.1(C-14),50.2(C-21),45.9(C-10),42.4(C-13),19.9(C-29),19.5(C-28),19.1(C-25),18.9(C-26),12.1(C-27),11.9(C-4)。该化合物的各种理化,波谱数据与对照品β-谷甾醇一致,故鉴定该化合物为β-谷甾醇。

化合物 4 白色粉末状固体 (氯仿-甲醇),mp.290～292℃,在磷钼酸,碘缸中显色。分子式为C35H60O6;E IMSm/z:550[M]+;I R(KBr)cm-1:3391(羟基),2959,2932,2868(饱和脂环氢 ),1642,1456,1377(碳碳双键),1107,1072,1022;13C NMR(CDCl3,125 MHz)δ:15.8(C-18),22.6(C-29),22.9(C-26),23.2(C-27),23.6(C-21),27.0(C-19),28.2(C-11),30.0(C-28),32.2(C-15),33.1(C-23),33.5(C-16),34.7(C-25),35.9(C-2),37.9(C-8),40.1(C-7),40.7(C-22),41.2(C-20),42.6(C-10),43.7(C-1),46.3(C-12),49.8(C-13),52.8(C-4),54.1(C-24),60.0(C-9),60.7(C-17),65.8(C-14),74.2(C-6′),77.5(C-4′),79.8(C-2′),80.4(C-3),81.2(C-3′),83.1(C-5′),105.1(C-1′),126.1(C-6),144.3(C-5)。其 IR和13C NMR与胡萝卜苷吻合,与胡萝卜苷对照品共薄层研值相同,与胡萝卜苷对照品混合,熔点不下降,故可鉴定该化合物为胡萝卜苷。

化合物 5 白色无定型粉末 (甲醇),mp.256～260℃,在碘缸,磷钼酸中显色,5%的硫酸显紫红色。分子式为 C30H48O3;EI-MSm/z:456[M]+;I R(KBr)cm-1:3431(OH),2965,2926,2870,1690(羰基),1456,1382,1033,998;1H NMR(CD3OD,500 MHz)δ:5.21(1H,t,H-12)且为环内双键,叔碳氢信号δ3.15(1H,m,H-3),2.20(1H,d,J=11.5 Hz,H-18)以及 5个甲基单峰 (1.10,0.98,0.94,0.83,0.76)和 2个甲基双峰 0.96(3H,d,J=4.0 Hz),0.87(3H,d,J=6.9 Hz)。13C NMR谱给出的 2个烯碳信号δ138.3(C-13)和 125.6(C-12),表明化合物为乌苏烷型五环三萜类化合物。13C NMR(CD3OD,125 MHz)δ:180.3(C-28),78.3(C-3),55.4(C-5),53.1(C-18),47.7(C-9),47.5(C-17),41.9(C-14),39.4(C-8),39.1(C-19),38.7(C-4),38.5(C-20),36.8(C-22),36.6(C-10),33.0(C-7),30.4(C-1),30.4(C-21),27.9(C-23),27.4(C-15),26.6(C-2),24.0(C-16),23.0(C-11),22.8(C-27),20.2(C-30),18.1(C-6),16.5(C-26),16.3(C-29),15.0(C-25),14.7(C-24)。理化常数和波谱数据与文献[7]报道一致,故鉴定该化合物为乌苏酸。

化合物 6 白色无定型粉末 (丙酮),mp.242～246℃,在紫外下不显色,在碘缸,磷钼酸中显色。分子式为 C30H48O4;EI-MSm/z:472[M]+;I R(KBr)cm-1:3440(OH),2965,2924,2870,1690(羰基),1458,1387,1254,1029,997;1H NMR(CD3OCD3,500 MHz)δ:5.19(1H,t,H-12),3.12(1H,ddd,H-2),2.85(1H,d,H-3),2.21(1H,d,H-18),0.75(3H,s,H-26),0.80(3H,s,H-24),0.85(3H,d,H-29),0.92(3H,d,H-30),0.93(3H,s,H-25),0.96(3H,s,H-23),1.10(3H,s,H-27);13C NMR谱给出的 2个烯碳信号 138.4(C-13)和 125.4(C-12),表明化合物为乌苏烷型五环三萜类化合物。13C NMR(CD3OCD3,125 MHz)δ:177.7(C-28),77.7(C-3),55.3(C-5),53.0(C-18),47.6(C-9),47.4(C-17),42.0(C-14),39.5(C-8),39.1(C-19),39.0(C-4),38.6(C-20),36.9(C-22),36.8(C-10),33.1(C-7),30.5(C-1),30.4(C-21),27.9(C-23),27.3(C-15),68.5(C-2),24.1(C-16),23.2(C-11),23.1(C-27),20.7(C-30),18.3(C-6),15.6(C-26),16.7(C-29),15.1(C-25),16.9(C-24)。理化常数和波谱数据与文献[8]报道一致,故鉴定该化合物为 2a,3β-二羟基乌苏酸。

化合物 7 无色结晶 (甲醇),mp.242～246℃,在紫外下不显色,在碘缸,磷钼酸中显色;C30H48O3;EI-MSm/z:456[M]+;I R(KBr)cm-1:3445,2941,1686,1456,1042;1H NMR(CD3OD,500 MHz)δ:4.69(1H,s),4.57(1H,s),0.73(3H,s),0.84(3H,s),0.93(3H,s),0.95(3H,s),0.98(3H,s),1.71(3H,s);13C NMR(CD3OD,125 MHz):δ:l3.8(C-24),l4.8(C-27),15.3(C-26),l5.4(C-25),18.1(C-6),l8.2(C-30),20.7(C-11),22.6(C-12),25.5(C-2),26.7(C-23),29.5(C-15),30.3(C-21),32.0(C-16),34.2(C-7),36.8(C-22),37.0(C-10),38.3(C-13),38.6(C-4),38.7(C-1),40.6(C-8),42.2(C-14),48.8(C-19),49.1(C-18),50.6(C-9),50.8(C-5),55.5(C-17),78.3(C-3),108.3(C-29),150.6(C-20),178.7(C-28),以上数据与文献[9]报道一致,故鉴定该化合物为白桦酸。

化合物 8 淡黄色粉末 (甲醇),在紫外、碘缸、磷钼酸中显色。分子式为 C18H16O8;ESI-MSm/z:359[M]+;IR(KBr)cm-1:3418,1697,1605,1521,1454,1265,1161,813;1H NMR(CD3OD,500 MHz)δ:7.01(1H,d,J=1.7 Hz,H-2),6.73(1H,d,J=3.45 Hz,H-5),6.91(1H,dd,J=8.6,1.7 Hz,H-6),7.49(1H,d,J=16.0 Hz,H-7),6.25(1H,d,J=16.0 Hz,H-8),6.66(1H,d,J=8.0 Hz,H-5′),6.59(1H,d,J=7.5 Hz,H-6′),3.07(1H,d,J=14.1 Hz,H-7′),2.95(1H,dd,J=14.1,8.9 Hz,H-7′),5.13(1H,d,J=8.5 Hz,H-8′)。13C NMR(CD3OD,125 MHz)δ:126.4(C-1),113.8(C-2),145.5(C-3),148.3(C-4),114.9(C-5),121.7(C-6),146.0(C-7),113.6(C-8),167.4(C-9),128.7(C-1′),116.2(C-2′),144.8(C-3′),143.8(C-4′),115.1(C-5′),120.4(C-6′),37.0(C-7′),78.1(C-8′),以上数据与文献[10]报道一致,可鉴定该化合物为迷迭香酸。

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Chemical Constituents in Herb ofSalvia cavalerieiLévl.

WANG He-ying,HU De-yu＊,XUEWei,YANG Song,SONGBao-an

Center for Research and Develop ment of Fine Chemicals,Key Laboratory of Green Pesticide and Agricultural B ioengineering,Ministry of Education,Guizhou University,Guiyang 550025,China

Q946.91;R284.1

A

1001-6880(2011)01-0063-03

2009-03-25 接受日期:2009-05-18

贵州省省长基金 2007[03],国家自然科学基金20662004,

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