澤漆的化學(xué)成分研究

何江波,劉光明,程永現(xiàn)

1中國科學(xué)院昆明植物研究所植物化學(xué)與西部植物資源持續(xù)利用國家重點(diǎn)實(shí)驗(yàn)室,昆明 650204;2大理學(xué)院,大理 671003

澤漆的化學(xué)成分研究

何江波1,2,劉光明2,程永現(xiàn)1＊

1中國科學(xué)院昆明植物研究所植物化學(xué)與西部植物資源持續(xù)利用國家重點(diǎn)實(shí)驗(yàn)室,昆明 650204;2大理學(xué)院,大理 671003

采用多種分離材料包括硅膠、Sephadex LH-20和反相 RP-18從澤漆的 95%乙醇提取物的正丁醇部位分離得到 12個(gè)化合物,經(jīng)過波譜學(xué)方法分別鑒定為 Helioscopin D(1),Isofraxidin(2),Swertiamarin(3),13-Carboxyblumenol C(4),4,4′-dimethoxy-3′-hydroxy-7,9′,7′9-diepoxyligan-3-O-β-D-glucopyranoside(5),(+)-Syringaresinol-4′-O-β-D-glucoside(6),2S,3R-2,3-Dihydro-2-(4-hydroxy-3-methoxyphenyl)-3-hydroxymethyl-7-methoxybenzofuran-5-(trans)propen-1-ol-3-O-β-glucoside(7),Quinquenin L1(8),(6R,9S)-megastigman-3-one-4,7-ene-9-ol-9-O-α-L-arabinofuranosyl-(1→6)-β-D-glucopyranoside(9),2R,3R-2,3-Dihydro-2-(4′-hydroxy-3′-methoxyphenyl)-3-(glucosyloxymethyl)-7-methoxy-benzofuran-5-propanol(dihydrodehydrodiconiferyl-alcohol-β-D-glucoside)(10),Thymidine(11),和 Deoxyuridine(12)。其中化合物 1為一個(gè)降倍半萜類新化合物,其余化合物從該種中首次分離。關(guān)鍵詞:澤漆;大戟科;化學(xué)成分

澤漆是大戟屬植物澤漆 (Euphorbia helioscopiaL.)的干燥全草,別名貓眼草、五朵云、五風(fēng)草,生于山坡、荒野、田邊及河岸邊,分布于除新疆和西藏以外的全國其它地方。澤漆性微寒,味苦,有毒,全草人藥,有利尿消腫、化痰散結(jié)、殺蟲止癢之功效,中醫(yī)及臨床常用其治療腹水、水腫、肺結(jié)核、痰多喘咳、癬瘡等疾病。據(jù)研究表明,其活性成分主要是二萜酯類和黃酮類成分。為了深入研究其化學(xué)成分,采用各種柱色譜從澤漆 95%乙醇提取物的正丁醇部位分離得到 12個(gè)化合物,化合物 1為新化合物,其余化合物均從該植物中首次分離得到。

1 實(shí)驗(yàn)部分

1.1 儀器及試劑

JASCO-20C型數(shù)字式旋光儀 (日本);FTS-135型紅外光譜儀 (KBr壓片,美國 B IO-RAD公司); UV210A型紫外可見光分度計(jì)(日本島津);VG AUTO Spec-3000(英國 VG公司)及 Finnigan MAT 90質(zhì)譜儀 (德國 Finnigan公司);Bruker AM-400及DRX-500 MHz核磁共振儀 (T MS作為內(nèi)標(biāo),δ為ppm,J為 Hz);200～300目柱色譜用硅膠、硅膠 H和 GF254薄層色譜用硅膠 (青島海洋化工廠);25～100μm Sephadex LH-20(Pharmacia公司);40～63 μm RP-18(日本Daiso)。石油醚、氯仿、丙酮、乙酸乙酯、甲醇等有機(jī)溶劑均為工業(yè)純經(jīng)重蒸后使用。

澤漆干燥全草,2008年 7月購于昆明市菊花村藥材市場(chǎng),經(jīng)云南省藥物研究所邱斌老師鑒定為大戟科澤漆Euphorbia helioscopiaL.的干燥全草,標(biāo)本(CHYX-0151)存于中國科學(xué)院昆明植物研究所植物化學(xué)與西部植物資源持續(xù)利用國家重點(diǎn)實(shí)驗(yàn)室。

1.2 提取與分離

澤漆干燥全草 15 kg,粉碎,95%乙醇回流提取3次,每次 2 h,低溫濃縮得到浸膏,加水懸浮后依次用石油醚、乙酸乙酯和正丁醇進(jìn)行萃取,合并正丁醇萃取液濃縮得到正丁醇部位 80 g。正丁醇部位上硅膠柱色譜(200～300目,1.5 kg)以氯仿-甲醇梯度洗脫得到 4個(gè)組份 (Fr.1～Fr.4),經(jīng)過硅膠柱色譜,氯仿-甲醇(20∶1)梯度洗脫,氯仿-丙酮 (10∶1)梯度洗脫、凝膠 SephadexLH-20(甲醇)柱色譜和反相 RP-18(甲醇-水:30%、50%、70%、90%)柱色譜由Fr.1得到化合物 5(20 mg)和 6(35 mg);Fr.2得到化合物 1(3 mg)、7(10 mg)和 8(12 mg);Fr.3得到化合物 2(5 mg)和 3(10 mg),11(12 mg),12(5 mg),Fr.4得到化合物 4(12 mg)、9(8 mg)和 10(12 mg)。化學(xué)結(jié)構(gòu)式見圖 1(Fig.1):

圖 1 化合物 1～12的結(jié)構(gòu)Fig.1 The structures of compounds 1-12

2 結(jié)構(gòu)鑒定

Helioscopin D(1) C14H26O4,無色油狀物,易溶于甲醇,:-1.8 (c0.6,MeOH);UV (MeOH):λmax(logε)=252(3.03),202(3.78); IR(KBr):νmax=3423,2964,2871,2309,1071 cm-1; ESI-MS(negative):m/z=293[M+Cl]-;HR-ESIMS(negative):m/z=293.1519[M+Cl]-(calcd. for C14H26O4Cl:293.1519)。計(jì)算其不飽和度為 2,從13C NMR譜可以看出,有 4個(gè)甲基,2個(gè)亞甲基,4個(gè)次甲基,3個(gè)季碳和 1個(gè)甲氧基,初步判斷為一個(gè)降倍半萜,通過文獻(xiàn)檢索發(fā)現(xiàn)其結(jié)構(gòu)與野鴉椿素B[1]相似,但是在 C-9的核磁數(shù)據(jù)有較小差異,所以推測(cè)是-OMe的連接位置不同所致。其平面結(jié)構(gòu)通過HMBC圖譜確定,HMBC圖譜可以得出 H-12(δH0.86)與 C-1,C-2,C-6,C-11相關(guān),H-11(δH1.18)與C-1,C-6,C-7,C-11相關(guān),H-13(δH1.15)與 C-4/C-5/C-6相關(guān),-OMe(δH3.31)與 C-9(δC79.9)相關(guān),因此其平面結(jié)構(gòu)得以鑒定?；衔?1的相對(duì)構(gòu)型通過ROESY圖譜確定,在 ROESY圖譜中,可以看到信號(hào) H-11與 H-3和 H-7相關(guān),因此 OH-3和 OH-6均為β構(gòu)型;當(dāng)單照射 H-13時(shí),發(fā)現(xiàn) H-4,H-7,H-8信號(hào)增益,因此可以判斷OH-5為α構(gòu)型,這一判斷通過與文獻(xiàn)[2]比較得到進(jìn)一步驗(yàn)證。H-7與 H-8的耦合常數(shù)為 15.9 Hz,表明雙鍵為反式。側(cè)鏈上 C-9的絕對(duì)構(gòu)型尚未能測(cè)定。化合物 1為新化合物,命名為 helioscopin D.1H NMR(500 MHz,CD3OD)δ: 1.64(1H,t,J=12.1 Hz,H-2a),1.45(1H,ddd,J= 12.1,4.0,2.0 Hz,H-2b),4.05(1H,m,H-3),1.76 (2H,m,H-4),6.11(1H,d,J=15.9 Hz,H-7),5.61 (1H,dd,J=15.9,7.9 Hz,H-8),3.86(1H,m,H-9),1.27(3H,d,J=6.3 Hz,H-10),1.18(3H,s,H-11),0.86(3H,s,H-12),1.15(3H,s,H-13),3.28 (3H,s,OMe);13C NMR(125 MHz,CD3OD)δ:40.7 (C-1),46.3(C-2),65.3(C-3),45.6(C-4),77.5 (C-5),79.2(C-6),134.7(C-7),133.5(C-8), 79.7(C-9),22.4(C-10),26.3(C-11),27.3(C-12),27.4(C-13),56.5(OMe).主要二維相關(guān)如下圖 2(Fig.2)。

圖2 化合物1的主要HMBC和ROESY相關(guān)Fig.2 ROESY and HMBC correlations for compound 1

Isofraxidin(2) 白色固體。1H NMR (500 MHz,CD3OD)δ:6.21(1H,d,J=9.5 Hz,H-3), 7.81(1H,d,J=9.5 Hz,H-4),6.95(1H,s,H-5), 3.91(3H,s,OMe),3.87(3H,s,OMe);13C NMR (125 MHz,CD3OD)δ:163.4(C-2),112.8(C-3), 146.5(C-4),112.2(C-4a),105.1(C-5),147.4 (C-6),144.7(C-7),136.2(C-8),145.6(C-8a), 56.9(OMe),61.7(OMe)。以上數(shù)據(jù)與文獻(xiàn)[3]數(shù)值相符。

Swertiamarin(3) 黃色油狀物。1H NMR (400 MHz,CD3OD)δ:5.69(1H,d,J=1.0 Hz,H-1),7.60(1H,s,H-3),1.70(1H,d,J=13.9 Hz,H-6a),1.88(1H,ddd,J=13.9,12.2,4.8 Hz,H-6b), 3.64(1H,d,J=5.6 Hz,H-7a),3.85(1H,dd,J= 11.9,1.6 Hz,H-7b),5.38(1H,m,H-8),2.88(1H, d,J=8.1 Hz,H-9),5.25(1H,dd,J=9.5,2.4 Hz, H-10a),5.35(1H,m,H-10b),4.60(1H,d,J=7.8 Hz,Glc,H-1),3.15-3.34(6H,m,Glc,H-2-H-6);13C NMR(100 MHz,CD3OD)δ:100.2(C-1),154.8 (C-3),108.8(C-4),64.3(C-5),33.7(C-6),66.0 (C-7),133.8(C-8),52.6(C-9),121.2(C-10), 168.0(C-11),99.1(Glc-1),77.8(Glc-2),74.4 (Glc-3),71.4(Glc-4),78.5(Glc-5),62.6(Glc-6)。以上數(shù)據(jù)與文獻(xiàn)[4]數(shù)值相符。

13-Carboxyblumenol C(4) 無色油狀物。ESI-MS(positive):[2M+Na]+=503;1H NMR (500 MHz,CD3OD)δ:2.08(1H,d,J=17.0 Hz,H-2a),2.58(1H,d,J=17.0 Hz,H-2b),6.48(1H,s, H-4),2.62(1H,t,J=6.4 Hz,H-6),1.37(1H,m, H-7a),1.98(1H,m,H-7b),1.50(2H,m,H-8), 3.66(1H,m,H-9),1.12(3H,d,J=6.0 Hz,H-10), 1.01(3H,s,H-11),1.13(3H,s,H-12).13C NMR (125 MHz,CD3OD)δ:37.5(C-1),48.1(C-2), 203.1(C-3),129.4(C-4),155.6(C-5),46.3(C-6),28.6(C-7),38.9(C-8),68.8(C-9),23.5(C-10),27.8(C-11),170.0(C-13),以上數(shù)據(jù)與文獻(xiàn)[5]數(shù)值相符。

4,4′-D imethoxy-3′-hydroxy-7,9′,7′9-diepoxyligan-3-O-β-D-glucopyranoside(5) 白色粉末。1H NMR(400 MHz,CD3OD)δ:6.93(1H,d,J=1.2 Hz,H-2),6.84(1H,d,J=1.2 Hz,H-2′),7.04 (1H,d,J=8.4 Hz,H-5),6.66(1H,d,J=8.4 Hz, H-5′),6.81(1H,dd,J=8.4,1.2 Hz,H-6),6.70 (1H,dd,J=8.4,1.2 Hz,H-6),4.64(1H,d,J= 3.6 Hz,H-7),4.59(1H,d,J=4.0 Hz,H-7′),3.01 (1H,m,H-8),3.01(1H,m,H-8′),4.12(2H,m,H-9),3.75(2H,m,H-9′),3.76(3H,s,OMe-4),3.74 (3H,s,OMe-4′),4.74(1H,d,J=6.0 Hz,Glc,H-1),3.20～3.40(4H,m,Glc,H-2～5),3.58(1H, m,Glc,H-6a),3,75(1H,m,Glc,H-6b);13C NMR (100 MHz,CD3OD)δ:137.4(C-1),111.5(C-2), 147.4(C-3),150.9(C-4),117.9(C-5),119.8(C-6),87.1(C-7),55.5(C-8),72.7(C-9),133.7 (C-1′),110.9(C-2′),147.3(C-3′),149.1(C-4′),116.0(C-5′),120.0(C-6′),87.0(C-7′),55.3 (C-8′),72.7(C-9′),102.7(Glc-1),74.9(Glc-2),77.8(Glc-3),71.2(Glc-4),78.2(Glc-5), 62.4(Glc-6),以上數(shù)據(jù)與文獻(xiàn)[6]數(shù)值相符。

(+)-Syringaresinol-4′-O-β-D-glucoside(6)白色粉末。1H NMR(500 MHz,CD3OD)δ:6.71(2H, s,H-2′,6′),6.65(2H,s,H-2′′,6′′),4.76(1H,d,J=3.2 Hz,H-2),4.70(1H,d,J=3.2 Hz,H-6),4.27 (2H,m,H-8),3.91(2H,dd,J=7.2,2.4 Hz,H-4), 3.76(1H,dd,J=12.0,2.0 Hz,H-6a),3.65(1H, dd,J=12.0,5.0 Hz,Glc,H-6b),3.47(1H,td,J= 7.1,2.2 Hz,Glc,H-5),3.41(2H,dd,J=7.1,2.2 Hz,Glc,H-4,H-3),3.19(1H,m,Glc,H-2),3.13 (2H,m,H-1,H-5),3.85(6H,s,OMe-2′,OMe-5′), 3.84(6H,s,OMe-2′′,OMe-5′′),4.85(1H,d,J= 7.7 Hz,Glc,H-1);13C NMR(125 MHz,CD3OD)δ: 55.5(C-1),55.7(C-5),72.8(C-4),72.9(C-8), 87.2(C-2),87.6(C-6),135.5(C-1′),133.0(C-1′′),104.4(C-2′),104.7(C-2′′),154.4(C-3′), 149.3(C-3′′),139.5(C-4′),136.1(C-4′′),154.4 (C-5′),149.3(C-5′′),104.4(C-6′),104.7(C-6′′),56.7(OMe),55.7(OMe),105.3(Glc-1), 75.7(Glc-2),77.8(Glc-3),71.3(Glc-4),78.2 (Glc-5),62.5(Glc-6)以上數(shù)據(jù)與文獻(xiàn)[7]數(shù)值相符。

2S,3R-2,3-D ihydro-2-(4-hydroxy-3-methoxyphenyl)-3-hydroxymethyl-7-methoxybenzofuran-5-(trans)propen-1-ol-3-O-β-glucoside(7) 無定形粉末。1H NMR(400 MHz,CD3OD)δ:6.92(1H, brs,H-6′),6.89(1H,J=2.0 Hz,H-2′),6.84(1H, d,J=1.4 Hz,H-2),6.77(1H,dd,J=8.0,1.4 Hz, H-6),6.75(1H,d,J=8.0 Hz,H-5),6.43(1H,d,J=16.0 Hz,H-7′),6.12(1H,dt,J=16.0,6.0 Hz, H-8′),5.52(1H,d,J=6.0 Hz,H-7),4.29(2H,d,J=6.0 Hz,H-9′),4.25(1H,d,J=8.0 Hz,Glc-1), 3.88(1H,dd,J=12.0,2.0 Hz,Glc-6a),3.72,3.77 (each 3H,s,OMe),3.74(1H,overlap,H-9a),3.68 (1H,dd,J=11.0,4.0 Hz,H-9b),3.58(1H,overlap,Glc-6b),3.19(1H,m,H-8),3.20(1H,overlap, Glc-3),3.15(1H,overlap,Glc-4),3.17(1H,m,Glc-5),3.18(1H,overlap,Glc-2);13C NMR(100 MHz, CD3OD)δ:134.5(C-1),110.6(C-2),149.1(C-3),147.5(C-4),116.1(C-5),119.7(C-6),89.3 (C-7),56.7(C-8),72.3(C-9),132.3(C-1′), 112.1(C-2′),145.5(C-3′),149.1(C-4′),130.1 (C-5′),131.9(C-6′),116.7(C-7′),134.2(C-8′),70.9(C-9′),55.1(OMe),56.4(OMe),103.1 (Glc-1),75.1(Glc-2),77.9(Glc-3),71.7(Glc-4),78.1(Glc-5),62.8(Glc-6),以上數(shù)據(jù)與文獻(xiàn)[8]數(shù)值相符。

Quinquen inL1(8) 白色粉末。1H NMR(400 MHz,CD3OD)δ:7.13(1H,brd,J=8.5 Hz,H-5′), 7.02(1H,d,J=1.7 Hz,H-2′),6.92(1H,dd,J= 8.5,1.7 Hz,H-6′),6.73(1H,s,H-4),6.71(1H, s,H-6),5.54(1H,d,J=6.0 Hz,H-2),3.85(3′-OMe),3.82(7-OMe),4.87(1H,d,J=7.8 Hz,Glc, H-1),3.40-3.80(6H,Glc-H);13C NMR(100 MHz, CD3OD)δ:88.5(C-1),55.7(C-3),138.4(C-3a), 114.2(C-4),129.6(C-5),118.1(C-6),145.2(C-7),147.5(C-7a),65.1(C-8),137.1(C-1′),111.2 (C-2′),147.6(C-3′),150.9(C-4′),117.9(C-5′),119.4(C-6′),35.8(C-1′′),32.9(C-2′′), 62.5(C-3′′),102.8(Glc-1),74.9(Glc-2),78.2 (Glc-3),71.3(Glc-4),77.9(Glc-5),62.2(Glc-6),56.7(7-OMe),56.8(3′-OMe),以上數(shù)據(jù)與文獻(xiàn)[9]數(shù)值相符。

(6R,9S)-megastigman-3-one-4,7-ene-9-ol-9-O-α-L-arabinofuranosyl-(1→6)-β-D-glucopyranoside(9) 無色粉末。1H NMR(500 MHz,CD3OD) δ:1.96(1H,d,J=17.6 Hz,H-2a),2.46(1H,d,J= 17.6 Hz,H-2b),5.88(1H,brs,H-4),2.70(1H,d,J=9.2 Hz,H-6),5.66(1H,dd,J=15.6,9.2 Hz,H-7),5.75(1H,dd,J=15.6,6.6 Hz,H-8),4.36 (1H,m,H-9),1.28(3H,d,J=6.5 Hz,H-10),1.00 (3H,s,H-11),1.08(3H,s,H-12),2.04(3H,d,J= 1.1 Hz,H-13),4.31(1H,d,J=7.9 Hz,Glc H-1), 3.13(1H,dd,J=9.0,7.9 Hz,Glc,H-2),3.34(1H, dd,J=9.0,9.0 Hz,Glc,H-3),3.24(1H,dd,J= 9.5,9.0 Hz,Glc,H-4),3.40(1H,m,Glc,H-5), 3.58(1H,dd,J=11.4,6.4 Hz,Glc,H-6a),3.98 (1H,dd,J=11.4,2.4 Hz,Glc,H-6b),4.96(1H, brs,Ara,H-1),3.94(1H,overlap,Ara,H-2),3.81 (1H,overlap,Ara,H-3),3.94(1H,overlap,Ara,H-4),3.63(1H,dd,J=11.8,5.3 Hz,Ara,H-5a),3.72 (1H,dd,J=11.8,3.3 Hz,Ara,H-5b);13C NMR (125 MHz,CD3OD)δ:37.4(C-1),48.1(C-2), 202.6(C-3),125.4(C-4),170.4(C-5),52.3(C-6),129.1(C-7),138.0(C-8),75.1(C-9),20.1 (C-10),29.1(C-11),27.6(C-12),25.1(C-13), 102.3(Glc-1),75.8(Glc-2),78.0(Glc-3),72.1 (Glc-4),76.7(Glc-5),68.2(Glc-6),109.9(Ara-1),83.1(Ara-2),78.9(Ara-3),85.9(Ara-4), 63.1(Ara-5),該化合物結(jié)構(gòu)與文獻(xiàn)[10]化合物相似,但首次歸屬了其核磁共振數(shù)據(jù)。

2R,3R-2,3-D ihydro-2-(4′-hydroxy-3′-methoxyphenyl)-3-(glucosyloxymethyl)-7-methoxybenzofuran-5-propanol(dihydrodehydrodicon iferylalcohol-β-D-glucoside)(10) 無色油狀物。1H NMR(500 MHz,CD3OD)δ:1.82(2H,brq,J=8.0 Hz,H-9),2.62(2H,brt,J=8.0 Hz,H-8),3.23 (1H,dd,J=9.0,8.5 Hz,H-2′′),3.27-3.40(3H, m,H-3′,H-4′,H-5′),3.56(2H,t,J=8.0 Hz,H-10),3.61-3.71(2H,m,H-3,H-6′a),3.79-3.90 (2H,m,H-11a,H-6′b),3.83(3H,s,OMe-3),3.86 (3H,s,OMe-3′),4.10(1H,dd,J=9.5,8.0 Hz,H-11b),4.35(1H,d,J=7.5 Hz,H-1′′),5.58(1H,d,J=6.0 Hz,H-2),6.72(1H,brs,H-4 or H-6),6.76 (1H,d,J=8.5 Hz,H-5′),6.80(1H,brs,H-6 or H-4),6.86(1H,dd,J=8.5,2.0 Hz,H-6′),7.00(1H, d,J=2.0 Hz,H-2′);13C NMR(125 MHz,CD3OD) δ:32.9(C-9),35.8(C-8),52.9(C-3),56.5 and 56.8(2×OMe),62.3(C-10),62.8(C-6′′),71.7 (C-4′),72.4(C-11),75.1(C-2′′),78.0(C-3′′), 78.2(C-5′′),89.2(C-2),104.3(C-1),111.0(C-2′),114.4(C-4 or C-6),116.1(C-5′),118.3(C-6 or C-4),119.8(C-6′),129.8(C-5),134.7(C-1′), 137.0(C-3a),145.2(C-7),147.5,147.9(C-7a,C-4′),149.0(C-3),以上數(shù)據(jù)與文獻(xiàn)[11]數(shù)值相符。

Thym idine(11) 淡黃色固體。1H NMR(400 MHz,CD3OD)δ:7.84(1H,s,H-6),6.30(1H,t,J=7.0 Hz,Rib,H-1),4.42(1H,td,J=5.9,3.3 Hz, Rib,H-4),3.92(1H,dd,J=3.3,3.5 Hz,Rib,H-3),3.83(1H,dd,J=12.0,3.3 Hz,Rib,H-5a),3.74 (1H,dd,J=12.0,3.3 Hz,Rib,H-5b),2.26(2H,m, Rib,H-2),1.90(3H,s,CH3);13C NMR(100 MHz, CD3OD)δ:152.4(C-2),166.5(C-4),111.5(C-5),138.2(C-6),88.8(Rib-1),41.4(Rib-2), 72.3(Rib-3),86.2(Rib-4),62.9(Rib-5),12.5 (5-CH3),以上數(shù)據(jù)與文獻(xiàn)[12]數(shù)值相符。

Deoxyurid ine(12) 淡黃色固體。1H NMR (400 MHz,CD3OD)δ:7.98(1H,d,J=8.1 Hz,H-6),5.68(1H,d,J=8.1 Hz H-5),6.26(1H,t,J= 7.0 Hz,Rib,H-1),2.27(2H,m,Rib,H-2),4.42 (1H,td,J=5.9,3.3 Hz,Rib,H-4),3.92(1H,dd,J=3.5,3.3 Hz,Rib,H-3),3.83(1H,dd,J=12.0, 3.3 Hz,Rib,H-5a),3.74(1H,dd,J=12.0,3.3 Hz, Rib,H-5b);13C NMR(100 MHz,CD3OD)δ:152.4 (C-2),166.5(C-4),102.7(C-6),142.5(C-5), 89.0(Rib-1),41.4(Rib-2),72.3(Rib-3),86.7 (Rib-4),62.9(Rib-5),以上數(shù)據(jù)與文獻(xiàn)[12]數(shù)值相符。

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Studies on the Chem ical Constituents ofEuphorbia helioscopia

HE Jiang-bo1,2,L IU Guang-ming2,CHENG Yong-xian1＊

1State Key Laboratory of Phytochem istry and Plant Resources in W est China,Kunm ing Institute of Botany,Chinese Academy of Sciences,Kunm ing 650204,China;2Dali College,Yunnan 671003,China

Twelve compounds including a new norsesquiterpenoid were isolated from the ethanol extractofEuphorbia helioscopiaby silica gel,sephadexLH-20 and RP-18 column chromatography.Theywere identified as helioscopin D(1), isofraxidin(2),s wertiamarin(3),13-carboxyblumenol C(4),4,4′-d imethoxy-3′-hydroxy-7,9′,7′9-diepoxyligan-3-O-β-D-glucopyranoside(5),(+)-syringaresinol-4′-O-β-D-glucoside(6),2S,3R-2,3-dihydro-2-(4-hydroxy-3-methoxyphenyl)-3-hydroxymethyl-7-methoxybenzofuran-5-(trans)propen-1-ol-3-O-β-glucoside(7),ouinquenin L1(8),(6R,9S)-megastigman-3-one-4,7-ene-9-ol-9-O-α-L-arabinofuranosyl-(1→6)-β-D-glucopyranoside(9),2R,3R-2,3-dihydro-2-(4′-hydroxy-3′-methoxyphenyl)-3-(glucosyloxymethyl)-7-methoxy-benzofuran-5-propanol(dihydrodehydrodiconiferyl-alcohol-β-D-glucoside)(10),thymidine(11),and deoxyuridine(12)on the basisofNMR data and comparison with literatures.

Euphorbia helioscopiaL;Euphorbiaceae;lignans

R284.2;Q946.91

A

1001-6880(2010)05-0731-05

2010-04-29 接受日期:2010-08-25

科技部“十一五”新藥創(chuàng)制重大專項(xiàng) (2008ZX09401-004);云南省中青年學(xué)術(shù)技術(shù)帶頭人基金 (2007PY01-48)

＊通訊作者 Tel:86-871-5223048;E-mail:yxcheng@mail.kib.ac.cn