筒鞘蛇菰化學(xué)成分研究

1、筒鞘蛇菰化學(xué)成分研究        【摘要】     目的研究蛇菰科筒鞘蛇菰Balanophora involicrata Hook.f.的化學(xué)成分。方法采用硅膠柱層析，Sephadex LH20，制備型薄層層析(PTLC)等技術(shù)手段分離純化單體，通過理化常數(shù)測定和光譜分析鑒定其化學(xué)結(jié)構(gòu)。結(jié)果從筒鞘蛇菰的石油醚和醋酸乙酯萃取部分，共分得8個(gè)化合物，即松柏苷(coniferin,),甲基松柏苷(methylconiferin,)，4OD葡萄糖吡喃型-松柏醛(4ODgl

2、ucopyranosyl coniferyl aldehyde，), 羽扇豆醇（lupeol，），乙酸羽扇豆醇酯(lupeol acetate，），香樹脂醇(amyrin，），谷甾醇(sitosterol，），胡蘿卜苷(sitosterol glucoside，）。結(jié)論 化合物為首次從該植物中分得。     【關(guān)鍵詞】  蛇菰科； 筒鞘蛇菰； 松柏醛    Studies on the Chemical Constituents of Balanophora involucrateLUO Bing， ZO

3、U Kun*， WANG Hui, TANG Zichun, YU Lingling(College of Chemistry ,China Central Normal University, Wuhan 430079，Hubei, China，Hubei Key Laboratory of Natural Products Research and Development, College of Chemistry and Life Sciences, China Three Gorges University, Yichang 443002, Hubei, China )Abstract

4、：ObjectiveThe chemical constituents of Balanophora involucrate Hook.f. were studied. MethodsConstituents were separated and repeatedly purified by means of column chromatography on silica gel column, Sephadex LH20 and preparative thin layer chromatography . Their structure was  elucidated by sp

5、ectral analysis. ResultsFrom the petrol ether and ethyl acetate extracts, eight compounds were obtained, their structures were elucidated as：coniferin(),mehtylconiferin(),4ODglucopyransyl coniferyl aldehyde(), lupeol(), lupeol acetate(), amyrin(), -sitosterol(), sitosterol glucoside() ConclusionComp

6、ound was obtained from this plant for the first time.Key words：Balanophoraceae；  Balanophora involucrate Hook.f.；  4ODglucopyransyl coniferyl aldehyde    筒鞘蛇菰Balanophora involucrate Hook.f.是蛇菰科蛇菰屬草本寄生植物，具有清熱解毒、涼血止血、益腎養(yǎng)陰的功效。主要用于治療肺熱咳嗽、咯血、血崩、痔瘡腫痛、腎虛腰痛、陽痿等癥。其化學(xué)成分報(bào)道較少13。本實(shí)驗(yàn)報(bào)道從其乙

7、醇提取物中分離并鑒定了8個(gè)化合物。分別為：松柏苷(coniferin,),甲基松柏苷(methylconiferin,)，4OD葡萄糖吡喃型-松柏醛(4OD-glucopyranosyl coniferyl aldehyde，), 羽扇豆醇（lupeol，），乙酸羽扇豆醇酯(lupeol acetate，），香樹脂醇(amyrin，），谷甾醇(sitosterol，），胡蘿卜苷(sitosterol glucoside，）。其中化合物為首次從該植物中分得。1  儀器和材料    X5精密顯微熔點(diǎn)儀(未校正)；Auatar Speltrometer ser

8、ies FT360型紅外分光光度儀；Bruker DRX500 核磁共振波譜儀；Finnigin電噴霧質(zhì)譜儀；Varian prostar 高效液相色譜儀；柱色譜用Sephadex LH20購自北京歐亞新技術(shù)公司；薄層色譜及柱色譜用硅膠均為青島海洋化工廠產(chǎn)品；AB8大孔吸附樹脂為天津南開大學(xué)化工廠產(chǎn)品。筒鞘蛇菰Balanophora involucrate Hook.f.采自湖北神農(nóng)架(經(jīng)三峽大學(xué)化學(xué)與生命學(xué)院陳發(fā)菊博士鑒定)。2  方法與結(jié)果2.1  提取和分離將筒鞘蛇菰藥材(全草)粉碎(1.8 kg),以95%的乙醇滲漉提取，合并總提取液，濃縮成浸膏，用水懸浮。分別以石

9、油醚、醋酸乙酯、正丁醇萃取，回收溶劑，得干燥浸膏分別為64.3，289.1，197.6 g。    經(jīng)反復(fù)硅膠柱層析，分別以石油醚醋酸乙酯，石油醚丙酮，氯仿甲醇梯度洗脫，以及Sephadex LH20柱層析，從石油醚部分得到4個(gè)化合物(30 mg)， (8mg)，(10mg)，(20mg)，醋酸乙酯部分得到4個(gè)化合物(150mg)，(20mg)，(25mg)，(16mg)。2.2  結(jié)構(gòu)鑒定2.2.1  化合物白色粉末， mp149151，1HNMR(MeOD,ppm)：3.423.90(6H,m,H2'6')3.89(3H,s

10、,OCH3),4.22(2H,d,J=5.50Hz,H9),4.90(1H,d,J=7.20Hz,H1'),6.28(1H,dt,J=15.85,5.5Hz,H8),6.56(1H,d,J=15.85Hz,H7),6.96(1H,dd,J=8.35,1.40Hz,H6),7.08(1H,d,J=1.40Hz,H-2),7.12(1H,d,J=8.35Hz,H5);13CNMR (CDCl3,ppm): 56.79(-OCH3)，62.56(C-6')，63.75(C9),71.38(C4'),74.94(C2'),77.87(C3'),78.24(C-5

11、'),102.82(C1'),111.51(C2),118.04(C5),120.79(C6),128.97(C8),131.32(C7),133.75(C1),147.67(C4),150.95(C3)。以上數(shù)據(jù)與文獻(xiàn)4比較數(shù)據(jù)一致,故鑒定化合物為松柏苷(coniferin)。2.2.2  化合物白色針狀晶體，mp193195，1HNMR(CD3OD,ppm)：3.203.90(6H,m,H2'-6'),3.30(3H,s,H11),3.83(3H,s,OCH3),4.17(2H,d,J=5.20Hz,H9),4.80(1H,d,J=7.30Hz,H

12、-1'),6.24(1H,dt,J=14.60,5.20Hz,H-8),6.49(1H,d,J=14.60Hz,H7),6.92(1H,dd,J=8.40,1.20Hz,H6),7.02(1H,d,J=1.20Hz,H2),7.05(1H,d,J=8.40Hz,H5)；13CNMR(CD3OD, ppm)：50.34(C11),57.17(OCH3),62.73(C6'),64.07(C-9),71.58(C4'),75.11(C2'),77.97(C3'),78.36(C5'),102.88(C1'),111.69(C2),117.94

13、(C5),121.25(C6),129.26(C8),131.68(C7),134.02(C1),147.71(C4),150.90(C3)。以上數(shù)據(jù)與文獻(xiàn)5比較數(shù)據(jù)一致,故鑒定化合物為甲基松柏苷(methylconiferin)。2.2.3  化合物白色粉末，mp212213, 1HNMR(DMSO,ppm)：3.203.90(6H,m,H2'6'),3.78(3H,s,OCH3),4.98(1H,d,J=6.8Hz,H-1'),6.69(1H,dd,J=16.0,8.0Hz,H-8),7.11(1H,d,J=8.4Hz,H6),7.25(1H,d,J=8.

14、4Hz,H5),7.30(1H,s,H2),7.63(1H,d,J=16.0Hz,H7),9.50(1H,d,J=8.0Hz,H9); 13CNMR(DMSO, ppm): 56.88(-OCH3),61.60(C-6'),70.52(C4'),73.96(C2'),77.04(C3'),77.47(C5'),100.45(C1'),112.61(C2),115.02(C5),116.16(C6),124.52(C8),127.77(C7),129.38(C1),149.90(C4),155.47(C3),197.11(C9)。以上數(shù)據(jù)與文獻(xiàn)5比

15、較數(shù)據(jù)一致。故鑒定化合物為4OD葡萄糖吡喃型松柏醛(4ODglucopyranosyl coniferyl aldehyde)。2.2.4  化合物白色晶體，mp175-176, 13CNMR(CDCl3)：14.8(C27),15.8(C24),16.2(C-26),17.0(C25),18.3(C6),18.6(C28),19.6(C30),21.2(C11),25.4(C12),27.5(C15),27.7(C2,C23),30.1(C21),34.5(C-7),35.8(C16),37.4(C13),38.8(C-1),39.0(C10),39.1(C4),40.0(C-22

16、),41.8(C8),43.1(C-14),43.3(C17),48.2(C19),48.6(C18),50.7(C9),55.4(C5),79.3(C3),109.6(C29),151.2(C20)。以上數(shù)據(jù)與文獻(xiàn)6比較數(shù)據(jù)一致,故鑒定化合物為羽扇豆醇（lupeol）。2.2.5  化合物白色粉末，mp125126, 13CNMR(CDCl3，ppm)：14.8(C27),16.2(C26),16.4(C25),16.7(C24),18.2(C6),18.4(C28),19.5(C30),21.2(C11),21.6(C2'),24.0(C2),25.3(C12),27.7

17、(C15),28.2(C23),30.1(C21),35.5(C7),35.8(C16),37.3(C13),38.0(C1),38.3(C10),38.6(C4),40.2(C22),41.1(C8),43.1(C14),43.2(C17),48.3(C19),48.5(C18),50.6(C9),55.6(C5),81.2(C3),109.6(C29),151.2(C20),171.2(C1')。以上數(shù)據(jù)與文獻(xiàn)7比較數(shù)據(jù)一致,故鑒定化合物為乙酸羽扇豆醇酯(lupeol acetate)。2.2.6  化合物白色晶體，mp187188, 13CNMR(CDCl3,ppm)：

18、15.6(C25),16.4(C24,26),18.6(C6),23.8(C11),23.9(C30),26.2(C27),26.4(C16),27.2(C15),28.2(C2),28.3(C28),28.7(C23),31.3(C21),32.7(C29),32.9(C17),33.6(C7),35.0(C20),37.2(C22),37.4(C10),38.3(C1),39.0(C4),40.3(C8),42.0(C14),47.1(C19),47.5(C18),47.9(C9),55.5(C5),79.3(C3),122.0(C12),145.4(C13)。以上數(shù)據(jù)與文獻(xiàn)2比較數(shù)據(jù)一致

19、,故鑒定化合物為香樹脂醇(amyrin)。2.2.7  化合物白色針狀晶體,mp136137,易溶于氯仿、醋酸乙酯,Liebermann-Burchard反應(yīng)呈陽性。IR(cm1)：3424(OH),2934,1463和1380(C=C),1062,957。將其與-谷甾醇標(biāo)準(zhǔn)品進(jìn)行薄層對照,Rf值相同,其紅外光譜亦與標(biāo)準(zhǔn)品的譜圖完全相同,故確定化合物為谷甾醇(sitosterol)。2.2.8  化合物白色粉末,mp280282,Liebermann-Burchard反應(yīng)呈陽性,Molish反應(yīng)呈陽性。IR(cm1)：3422(OH),2932,2868,1627(C=C),1461,1380,1161,799,618, 將其與胡蘿卜苷標(biāo)準(zhǔn)品進(jìn)行薄層對照,Rf值相同,其紅外光譜亦與胡蘿卜苷標(biāo)準(zhǔn)品的譜圖完全相同,另外其1HNMR譜與文獻(xiàn)8對照亦基本一致,故確定化合物為胡蘿卜苷(sitosterol glucoside)。3  討論    通過以上的研究基本弄清了簡鞘蛇菰所含的主要化學(xué)成分，為今后進(jìn)一步研究其藥物活性奠定了基礎(chǔ)。    【參考文獻(xiàn)】  1 沈小玲，胡英杰，沈 勝 ，等.筒鞘蛇菰的