貴州鼠尾草化學(xué)成分的研究

王和英,胡德禹,薛 偉,楊 松,宋寶安

貴州大學(xué)精細(xì)化工研究開發(fā)中心教育部綠色農(nóng)藥與生物工程重點(diǎn)實(shí)驗(yàn)室,貴陽(yáng) 550025

貴州鼠尾草化學(xué)成分的研究

王和英,胡德禹＊,薛 偉,楊 松,宋寶安

貴州大學(xué)精細(xì)化工研究開發(fā)中心教育部綠色農(nóng)藥與生物工程重點(diǎn)實(shí)驗(yàn)室,貴陽(yáng) 550025

從貴州鼠尾草 95%乙醇提取物分離得到 8個(gè)化合物,通過(guò)理化性質(zhì)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(xué)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(shù)的 20%,宜生長(zhǎng)于溫?zé)釒У貐^(qū)[1]。我國(guó)鼠尾草植物品種,據(jù)《中國(guó)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(guó)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(lái),隨著對(duì)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(yīng)用也有了廣泛的發(fā)展。而到目前為止貴州鼠尾草化學(xué)成分國(guó)內(nèi)還沒有相關(guān)報(bào)道,因此我們對(duì)貴州鼠尾草化學(xué)成分進(jìn)行了研究,從其全草 95%乙醇提取物中分離得到 8個(gè)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(shù)字顯微熔點(diǎn)測(cè)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(nèi)標(biāo));HPMS 5973質(zhì)譜儀 (美國(guó)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(jīng)貴陽(yáng)醫(yī)學(xué)院藥學(xué)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(biāo)本保存于貴州大學(xué)精細(xì)化工研究開發(fā)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(wú)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(jīng)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(jīng)反復(fù)硅膠柱層析分離,分別用石油醚-乙酸乙酯系統(tǒng) (1∶0～1∶1),氯仿 -甲醇系統(tǒng) (1∶0～0∶1)進(jìn)行梯度洗脫。經(jīng)多次柱色譜分離,純化和重結(jié)晶,最后分離得到 8個(gè)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(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[6]報(bào)導(dǎo)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(guò) I R,1H NMR,13C NMR與質(zhì)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(huán)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(shù)據(jù)與對(duì)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(huán)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(duì)照品共薄層研值相同,與胡蘿卜苷對(duì)照品混合,熔點(diǎn)不下降,故可鑒定該化合物為胡蘿卜苷。

化合物 5 白色無(wú)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(huán)內(nèi)雙鍵,叔碳?xì)湫盘?hào)δ3.15(1H,m,H-3),2.20(1H,d,J=11.5 Hz,H-18)以及 5個(gè)甲基單峰 (1.10,0.98,0.94,0.83,0.76)和 2個(gè)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(gè)烯碳信號(hào)δ138.3(C-13)和 125.6(C-12),表明化合物為烏蘇烷型五環(huán)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(shù)和波譜數(shù)據(jù)與文獻(xiàn)[7]報(bào)道一致,故鑒定該化合物為烏蘇酸。

化合物 6 白色無(wú)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(gè)烯碳信號(hào) 138.4(C-13)和 125.4(C-12),表明化合物為烏蘇烷型五環(huán)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(shù)和波譜數(shù)據(jù)與文獻(xiàn)[8]報(bào)道一致,故鑒定該化合物為 2a,3β-二羥基烏蘇酸。

化合物 7 無(wú)色結(jié)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(shù)據(jù)與文獻(xiàn)[9]報(bào)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(shù)據(jù)與文獻(xiàn)[10]報(bào)道一致,可鑒定該化合物為迷迭香酸。

1 Chang JM(常軍民 ),Zhu NS(諸年生 ),Wang XL(王新玲),et al.Advances in the research of chemical constituents ofSalvia.Chin Tradit Patent Med(中成藥),1999,21:480-482.

2 Wang XL(王新玲 ),Chang JM(常軍民 ),Zhu NS(諸 年生),et al.Advances in the research of chemical constituents ofSalvia.J Xinjiang Med Univ(新疆醫(yī)科大學(xué)學(xué)報(bào)),2002,25:235-237.

3 Lin HC,ChangWL,et al.Diterpenoids fromSalvia mihiorrhiza.Phytoche mistry,2000,53:951-953.

4 Georgianne-Valli MD,Elsa-Grace V,Giardina MD,et al.Effects and drug interactions of herbal therapieswith cardiovascular effects.J Am Coll Cardio,2002,39:1083-1095.

5 Topcu G,Turkmen Z,Ulubelen A,et al.Highly hydrox.ylated triterpenes fromSalvia kronenburgii.J Nat Prod,2004,67:118-121.

6 Chang JM(常軍民),Zhu NS(諸年生),et al.The research of chemical constituents ofSalvia desertaSchang,Nat Prod Res Dev(天然產(chǎn)物研究與開發(fā)),2001,13:27-29.

7 Wang XM(王曉明),Xie CB(謝從炳),Wang L(王磊 ),et al.Studies on the chemical constituents fromSalvia plectranthoidesGriff,J Huazhong Univ Sci Tech(華中科技大學(xué)學(xué)報(bào)),2002,31:254-255.

8 ChengB(陳斌 ),ZhuM(朱梅 ),et al.To study the chemical constituents from the roots and rhizomes ofGerbera piloselloides.Chin J Chin Mat Med(中國(guó)中藥雜志),2002,27:596-597.

9 Lv TS(呂泰省),Mao SL(毛士龍),et al.The triterpenes in Cassia siamea Lam..Acad J Second Mil Med Univ(第二軍醫(yī)大學(xué)學(xué)報(bào)),2001,22:241-241,244.

10 Zhang ZF(張正付),Chen HS(陳鴻珊),LiJR(李健蕊),et al.Studies on polyphenolic chemical constitutents from root ofSalvia yunnansis.Chin J Chin Mat Med(中國(guó)中藥雜志),2007,32:1886-1890.

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(zhǎng)基金 2007[03],國(guó)家自然科學(xué)基金20662004,

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