716藥學(xué)學(xué)報(bào) Acta Pharmaceutica Sinica2004,39(9):716-718石膽草中的一個(gè)新苯乙醇苷鄭曉珂,劉云寶,李軍,馮衛(wèi)生(河南中醫(yī)學(xué)院,河南鄭州450008)摘要:目的研究石膽草( Corallodiscus flabellata)乙酸乙酯部位的化學(xué)成分。方法利用 Diaion HP-20Sephadex凵H20,硅膠柱等色譜技術(shù)進(jìn)行分離純化,根據(jù)化合物的理化性質(zhì)和光譜數(shù)據(jù)鑒定結(jié)構(gòu)。結(jié)果分離并鑒定了4個(gè)化合物:1·04βD(3,4二羥基苯乙基)60-香草?；咸擒?1);1·O-9-(4羥基苯乙基)βD芹糖-(L→2)葡糖苷(2);4羥基苯乙醇(3);,1’·二羥基乙醚(4)。結(jié)論化合物1為新化合物,化合物2-4均首次從該植物中分離得到。關(guān)鍵詞:苦苣苔科;石膽草;苯乙醇背;結(jié)構(gòu)鑒定中圖分類號:R284.1;R284.2文獻(xiàn)標(biāo)識碼:A文章編號:0513-4870(2004)09-0716-03One new phenylethanoid glycoside from Corallodiscus flabellataZHENG Xiao-ke, LIU Yun-bao, LI Jun, FENG Wei-shengHenan College of Traditiona Chinese Medicine, Zhengzhou 450008, ChiAbstract:Aim to study the antivirus chemical constituents of Corallodiscus flabellata. MethodsThe compounds were isolated with macroporous absorption resin, Diaion HP-20, Sephadex LH-20, silicagel column chromatography and identified on the basis of their physio-chemical and spectral data. ResultsFour compounds were obtained and identified as 1-0-B-D-(3, 4-dihydroxyphenyl )-ethyl-6-0-vanilloylglucopyranoside(1); 1'-0-B-(4-hydroxyphenyl)-ethyl-B-D-apiofuranosyl-(1-2)-glucopyranNside(2);compound, compounds 2-4 were isolated from Corallodiscus flabellata for the first time ound 1 is a new4. hydroxyphenethyl alcohol (3) bis(2-hydroxyethyl)ether(4). Conclusion CompKey words: Gesneriaceae; Corallodiscus flabellata: phenylethanoid glycoside; structuralidentification石膽草( Corallodiscus flabellata)為苦苣苔科發(fā)價(jià)值。為全面深人闡明其藥效物質(zhì)基礎(chǔ),本文繼( Gesneriaceae珊瑚苣苔屬( Corallodiscus)植物石膽續(xù)報(bào)道從其乙酸乙酯部位分離并鑒定的4個(gè)化合草的全草,有活血解毒、消腫止痛、清熱除濕的功物,分別為:1·0BD(3,4·二羥基苯乙基)60效{。作者利用 Diaion HP20, Sephadex LH20,硅香草?；咸擒?1);l·OB-(4羥基苯乙基)β膠柱等色譜技術(shù)對石膽草化學(xué)成分進(jìn)行了系統(tǒng)研D芹糖(1→2)葡糖苷(2);4羥基苯乙醇(3);1究2-”,發(fā)現(xiàn)石膽草的主要成分為苯乙醇苷類該類1二羥基乙醚(4)。其中化合物1為新化合物,化化學(xué)成分具有較強(qiáng)的抗炎抗病毒活性,有極大的開合物2~4為首次從該植物中分離得到。化合物1白色無定形粉末,具吸濕性。易溶收稿日期:200309-15于H2O和MeOH,可溶于Me2CO,遇FeCl2基金項(xiàng)日:河南省高校杰出科研人才創(chuàng)新工程資助項(xiàng)目K[Fe(CN)6]試劑顯藍(lán)色,為酚性物質(zhì)薄層板上(2003KY(XO02);河南省杰出青年科學(xué)基金資助項(xiàng)目(0212001200)酸水解檢識到葡萄糖,說明此化合物為一含葡萄糖通訊作者Tel:86-371-568069,fax:86-371-568001,的苷。高分辨質(zhì)譜( HRFAB-Ms)m/:465.1407[(M-1)-,C2H2O1,計(jì)算值:465.1402]。鄭曉珂等:石膽草中的一個(gè)新苯乙醇苷717HNMR譜中芳香區(qū)共6個(gè)氫,87.59(1H,d,J=色譜填充劑所用 Diaion HP20, Toyupearl HW40系84,1.6Hz),7.52(1H,d,J=1.6Hz),6.88(1H,日本三菱公司生產(chǎn), Sephadex Li20凝膠為d,J=8.4Hz)這3個(gè)氫組成一個(gè)ABX系統(tǒng);86.73 Pharmacia產(chǎn)品。實(shí)驗(yàn)所用硅膠均由青島海洋化工(1H,d,J=1.6H),6.68(1H,d,J=8.0Hz),6.51廠生產(chǎn)(IH,dd,J=8.0,1,6H),這3個(gè)氫也組成-個(gè)石膽草全草采自河南省西峽縣,經(jīng)河南中醫(yī)學(xué)ABX系統(tǒng),說明分子中存在兩個(gè)苯環(huán)且均為1,3,4院標(biāo)本室劉若庸教授鑒定為苦苣苔科三取代。δ2.75出現(xiàn)一雙氫多重峰為苯乙醇苷元7( Gesneriaceae)珊瑚苣苔屬( Corallodiscus)植物石膽位上的兩個(gè)氫特征信號,8379(3H,s)為甲氧基信草( Corallodiscus abellata)的全草,標(biāo)本存放于本研號,84.37(IH,d,J=7.6Hz)為葡萄糖的端基氫信究室(編號為200001號,并根據(jù)偶合常數(shù)(J=7.6Hx)確定其為β構(gòu)1提取與分離型。"CNMR譜中,共出現(xiàn)22個(gè)碳峰除苯乙醇苷元石膽草全草20kg,用水煎煮兩次(2h/次),合和葡萄糖的14個(gè)碳外,還有8個(gè)碳峰,δ166.4,并濾液減壓濃縮得總浸膏1860g,浸膏加入適量水151.9,147.9,124.5,122.4,116.7,12.9,56.0,分散,依次用E2O,EOAc,n-BuOH萃取至無色,各這一組數(shù)據(jù)與香草酸( vanillic acid)的碳譜數(shù)據(jù)相部分減壓濃縮萃取液得到E2O, EIOAc,n-BuOH和致,推測可能含有香草?；?。結(jié)合 H-H COSY H2O,殘留物。將EOAc部分110g水溶解后通過和HNMR譜,確定gH的兩個(gè)氫分別出現(xiàn)在8大孔吸附樹脂 Diaion HP20柱依次用H2O,10%,466(1H,dd,y=12.0,2.0H2),δ4.32(1H,d,20%,30%MeOH…70%Me2CO洗脫,Dion柱的」=124,6.8Hz)位于低場,且guC6出現(xiàn)在820%MeOH洗脫部分(15.0g)通過 Sephadex LH2064.7,提示葡萄糖的6位被?；瘬?jù)此推斷香草酰基柱,用H2O洗脫及10%MeOH洗脫,10%MeOH洗連接在葡萄糖的6位。HMBC譜中葡萄糖6位兩個(gè)脫物通過硅膠柱色譜( EtOAc-EtOH-H2O15:2:1)質(zhì)子(84.64.32)與香草?；械聂驶鵆(6得到化合物1(18mg), Diaion柱的30%MeOH洗166.4)均有相關(guān)峰,進(jìn)一步證明香草酰基連接在葡脫部分(10.0g)通過 Sephadex LH20柱,用水洗脫萄糖的6位。葡萄糖的端基質(zhì)子(δ4.37)與3,4-二洗脫物再經(jīng)硅膠柱色譜,CHCl3-MeOH-H2O(3:1羥基苯乙醇的8位C(871.4)有相關(guān)崢,因此確定0.1)洗脫.得化合物2(30mg),CHCl3MeOH-H2O苯乙醇8位C與葡萄糖的端基相連。利用HH(6:l:0.1)洗脫得化合物3(25mg),4(80mgCosY和HMQC對各碳?xì)溥M(jìn)行了歸屬(表1)。綜上2結(jié)構(gòu)鑒定分析,確定化合物1的結(jié)構(gòu)為10B-D-(3,4-二羥化合物1白色無定形粉末,具吸濕性。易溶基苯乙基)460-香草?；咸擒誟10-B-D-(3,4-于H20,MeOH,可溶于M2CO,遇FeCdihydroxypher)eh60 anilloyl-glucopyranoside]。K3[Fe(CN)]試劑顯藍(lán)色。m145-147℃經(jīng)文獻(xiàn)檢索未見報(bào)道確定為新化合物(圖1)。[a]3-42.1°(MOH,c0.41)。高分辨質(zhì)譜HRFAB-MS )m/z: 465 1407[(M-H)C2H2QO1,計(jì)算值:465.1402]。UV入m285.3。IR(KBr壓片)cm-:3487,3228,2927,1701,1602,1516,1286,1222,1079,763。HNMR,CNMR數(shù)據(jù)見表1Figure 1 Structure of compound 1化合物2白色無定形粉末,具吸濕性。易溶于H2O,MeOH,可溶于Me2CO,遇FeCl2實(shí)驗(yàn)部分K[Fe(CN)6]試劑顯藍(lán)色。ES-Msm/2:432.2。Kofler顯微測熔儀(未經(jīng)校正); Shimadzu PCHNMR(400 MHz, in MeOD)8: 7. 04(2H,d, J8201紅外光譜儀(KBr壓片); Shimadzu uv-vs28.4Hz,H-2,6),6,68(2H,d,=8.4Hz,H3,5)紫外分光光度計(jì); Perkin Elemeb Polarimeter34微5.37(1H,J=2Hz,api-1),4.32(1H,d,J=7.6Hz量旋光儀。APEXⅡ型傅立葉變換離子回旋質(zhì)譜g),4.02(1H,m,aH),3.6(1H,m,a-H'),2.80儀; Bruker dpx400型核磁共振儀,mMS為內(nèi)標(biāo);柱(21,t,=76HBH),40~325(10H,糖上H)。CNMR(100MHz, in MeOD)8:15.8(C4),131.0718藥學(xué)學(xué)報(bào) Acta Pharmaceutica Sinica2004,39(9):716-718(C2,.6),130.8(C-1),16.1(C-3,5),11.5(api-t,J=7.2H,BH),2.70(2H,t,J=7.2H,aH)1),103.3(μ-1),80.7(api-3),78.7(gu2),78.0cNMR(0oMHz, acetone-d)8:156.3(C4)(api-2),78(g如u3),754(api4),72.0(}4),130.9(C1),130.6(C2,6),117(C3,5),61.171.7(β-C),662(api5),62.8(cu6),36.5(a-C)。(β-C),39.3(aC)。根據(jù)以上數(shù)據(jù)確定該化合物為以上數(shù)據(jù)與文獻(xiàn)報(bào)道的1OB-(4.羥基苯乙基)B-4羥基苯乙醇D芹糖+(1-2)-葡糖苷6一致,為已知化合物?；衔?無色粘稠狀液體。遇茴香醛硫酸試劑顯淡紅色。ESI-MSm/z:106.1。HNMR(400Table 1 NMR spectral data of compound 1 MHz, acetone-d6 )8: 3. 60(2H, I, J=4. 2 Hz), 3. 50acetone-ds)(2H. t, J=4.2 Hz, ).CNMR(100 MHz, acetoneDEPTd4)8:7.2,618。根據(jù)以上數(shù)據(jù)確定該化合物為1,1′二羥基乙醚。1130.9致謝:核磁共振譜、紅外光譜由鄭州大學(xué)分析測試中115.76.73(IH,d,J=1.6Hz)心代測,質(zhì)譜由中國科學(xué)院化學(xué)研究所質(zhì)譜中心代測45.514415.46.68(1H,d,J=8.0Hz)References120.86.51(1H,dd,J=80,1.6Hz)CH3622.75(2H,m)[1 Jiangsu New Medical College. 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