貴州鼠尾草化學成分的研究

王和英,胡德禹,薛 偉,楊 松,宋寶安

貴州大學精細化工研究開發中心教育部綠色農藥與生物工程重點實驗室,貴陽 550025

貴州鼠尾草化學成分的研究

王和英,胡德禹＊,薛 偉,楊 松,宋寶安

貴州大學精細化工研究開發中心教育部綠色農藥與生物工程重點實驗室,貴陽 550025

從貴州鼠尾草 95%乙醇提取物分離得到 8個化合物,通過理化性質及波譜方法分別鑒定為正三十三烷(1),十二烷酸十四烷酯 (2),β-谷甾醇 (3),胡蘿卜苷 (4),烏蘇酸 (5),2a,3β-二羥基烏蘇酸 (6),白樺酸 (7)和迷迭香酸 (8)。以上化合物均首次從該植物中分離得到。

貴州鼠尾草;化學成分

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

鼠尾草為唇形科 (Labiatae)鼠尾草屬 (Salvia)植物。鼠尾草屬植物全球有 900種,占全科植物總數的 20%,宜生長于溫熱帶地區[1]。我國鼠尾草植物品種,據《中國藥物志》記載有 83種,25變種,9變型,其中藥用 30余種 (含變種,變型),分布于全國各地[2]。貴州鼠尾草 (Salvia cavalerieiLévl)別名:朱砂草,血盆草,反背紅,葉下紅等,是貴州民間中草藥,在民間是一味常用的中草藥,治療范圍廣,療效確切。其主要作用有有涼血解毒,散瘀止血等功效。近年來,隨著對鼠尾草屬植物活性成分及藥理作用研究[3-5]的深入,鼠尾草植物在臨床的應用也有了廣泛的發展。而到目前為止貴州鼠尾草化學成分國內還沒有相關報道,因此我們對貴州鼠尾草化學成分進行了研究,從其全草 95%乙醇提取物中分離得到 8個化合物,所得化合物均首次從該植物中分離得到。

1 儀器和試劑

X-4型數字顯微熔點測定儀 (溫度未校正);日本電子 JOEL-ECX500型 500 MHz核磁共振儀 (T MS為內標);HPMS 5973質譜儀 (美國惠普公司)。柱色譜硅膠及薄層色譜硅膠均為青島海洋化工出品;所用試劑均為分析純。

貴州鼠尾草采自貴州省興義市,經貴陽醫學院藥學院教研室主任龍慶德鑒定為唇形科鼠尾草屬植物貴州鼠尾草 (Salvia cavalerieiLévl),標本保存于貴州大學精細化工研究開發中心。

2 提取分離

曬干的貴州鼠尾草全草 11 kg粉碎后,用 95%的乙醇加熱回流提取三次,每次 2 h,合并提取液,減壓濃縮至無醇味得稠浸膏 1258 g。加水使成混懸液,依次用石油醚,乙酸乙酯,正丁醇萃取,合并各萃取液并經減壓濃縮,分別得石油醚萃取物 208 g,乙酸乙酯萃取物 171 g,正丁醇萃取物 106 g。萃取物經反復硅膠柱層析分離,分別用石油醚-乙酸乙酯系統 (1∶0～1∶1),氯仿 -甲醇系統 (1∶0～0∶1)進行梯度洗脫。經多次柱色譜分離,純化和重結晶,最后分離得到 8個化合物,分別為正三十三烷 (65 mg),十二烷酸十四烷酯 (37 mg),β-谷甾醇 (102 mg),胡蘿卜苷 (218 mg),烏蘇酸 (550 mg),2a,3β-二羥基烏蘇酸 (85 mg),白樺酸 (22 mg)和迷迭香酸 (28 mg)。

3 結構鑒定

化合物 1 白色固體 (氯仿),mp.68～70℃,在紫外,磷鉬酸,碘缸中均不顯色。分子式為 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),上述光譜數據與文獻[6]報導一致,可鑒定該化合物為正三十三烷。

化合物 2 白色固體 (氯仿),mp.60～64℃,在紫外,磷鉬酸,碘缸中均顯色。分子式為 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),通過 I R,1H NMR,13C NMR與質譜可鑒定該化合物為十二烷酸十四烷酯。

化合物 3 白色針狀固體 (氯仿),mp.132.2～132.9℃,在磷鉬酸,碘缸中顯色。分子式為 C29H50O;E IMSm/z:414[M]+;IR(KBr)cm-1:3426(羥基),2959,2866(飽和脂環氫),1458,1375(碳碳雙鍵);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)。該化合物的各種理化,波譜數據與對照品β-谷甾醇一致,故鑒定該化合物為β-谷甾醇。

化合物 4 白色粉末狀固體 (氯仿-甲醇),mp.290～292℃,在磷鉬酸,碘缸中顯色。分子式為C35H60O6;E IMSm/z:550[M]+;I R(KBr)cm-1:3391(羥基),2959,2932,2868(飽和脂環氫 ),1642,1456,1377(碳碳雙鍵),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與胡蘿卜苷吻合,與胡蘿卜苷對照品共薄層研值相同,與胡蘿卜苷對照品混合,熔點不下降,故可鑒定該化合物為胡蘿卜苷。

化合物 5 白色無定型粉末 (甲醇),mp.256～260℃,在碘缸,磷鉬酸中顯色,5%的硫酸顯紫紅色。分子式為 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)且為環內雙鍵,叔碳氫信號δ3.15(1H,m,H-3),2.20(1H,d,J=11.5 Hz,H-18)以及 5個甲基單峰 (1.10,0.98,0.94,0.83,0.76)和 2個甲基雙峰 0.96(3H,d,J=4.0 Hz),0.87(3H,d,J=6.9 Hz)。13C NMR譜給出的 2個烯碳信號δ138.3(C-13)和 125.6(C-12),表明化合物為烏蘇烷型五環三萜類化合物。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)。理化常數和波譜數據與文獻[7]報道一致,故鑒定該化合物為烏蘇酸。

化合物 6 白色無定型粉末 (丙酮),mp.242～246℃,在紫外下不顯色,在碘缸,磷鉬酸中顯色。分子式為 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譜給出的 2個烯碳信號 138.4(C-13)和 125.4(C-12),表明化合物為烏蘇烷型五環三萜類化合物。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)。理化常數和波譜數據與文獻[8]報道一致,故鑒定該化合物為 2a,3β-二羥基烏蘇酸。

化合物 7 無色結晶 (甲醇),mp.242～246℃,在紫外下不顯色,在碘缸,磷鉬酸中顯色;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),以上數據與文獻[9]報道一致,故鑒定該化合物為白樺酸。

化合物 8 淡黃色粉末 (甲醇),在紫外、碘缸、磷鉬酸中顯色。分子式為 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′),以上數據與文獻[10]報道一致,可鑒定該化合物為迷迭香酸。

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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

貴州省省長基金 2007[03],國家自然科學基金20662004,

＊通訊作者 Tel:86-851-3620521;E-mail:jhzx.msm@gmail.com