泽漆的化学成分研究

何江波,刘光明,程永现

1中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室,昆明 650204;2大理学院,大理 671003

泽漆的化学成分研究

何江波1,2,刘光明2,程永现1＊

1中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室,昆明 650204;2大理学院,大理 671003

采用多种分离材料包括硅胶、Sephadex LH-20和反相 RP-18从泽漆的 95%乙醇提取物的正丁醇部位分离得到 12个化合物,经过波谱学方法分别鉴定为 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为一个降倍半萜类新化合物,其余化合物从该种中首次分离。关键词:泽漆;大戟科;化学成分

泽漆是大戟属植物泽漆 (Euphorbia helioscopiaL.)的干燥全草,别名猫眼草、五朵云、五风草,生于山坡、荒野、田边及河岸边,分布于除新疆和西藏以外的全国其它地方。泽漆性微寒,味苦,有毒,全草人药,有利尿消肿、化痰散结、杀虫止痒之功效,中医及临床常用其治疗腹水、水肿、肺结核、痰多喘咳、癣疮等疾病。据研究表明,其活性成分主要是二萜酯类和黄酮类成分。为了深入研究其化学成分,采用各种柱色谱从泽漆 95%乙醇提取物的正丁醇部位分离得到 12个化合物,化合物 1为新化合物,其余化合物均从该植物中首次分离得到。

1 实验部分

1.1 仪器及试剂

JASCO-20C型数字式旋光仪 (日本);FTS-135型红外光谱仪 (KBr压片,美国 B IO-RAD公司); UV210A型紫外可见光分度计(日本島津);VG AUTO Spec-3000(英国 VG公司)及 Finnigan MAT 90质谱仪 (德国 Finnigan公司);Bruker AM-400及DRX-500 MHz核磁共振仪 (T MS作为内标,δ为ppm,J为 Hz);200～300目柱色谱用硅胶、硅胶 H和 GF254薄层色谱用硅胶 (青岛海洋化工厂);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、甲醇等有机溶剂均为工业纯经重蒸后使用。

泽漆干燥全草,2008年 7月购于昆明市菊花村药材市场,经云南省药物研究所邱斌老师鉴定为大戟科泽漆Euphorbia helioscopiaL.的干燥全草,标本(CHYX-0151)存于中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室。

1.2 提取与分离

泽漆干燥全草 15 kg,粉碎,95%乙醇回流提取3次,每次 2 h,低温浓缩得到浸膏,加水悬浮后依次用石油醚、乙酸乙酯和正丁醇进行萃取,合并正丁醇萃取液浓缩得到正丁醇部位 80 g。正丁醇部位上硅胶柱色谱(200～300目,1.5 kg)以氯仿-甲醇梯度洗脱得到 4个组份 (Fr.1～Fr.4),经过硅胶柱色谱,氯仿-甲醇(20∶1)梯度洗脱,氯仿-丙酮 (10∶1)梯度洗脱、凝胶 SephadexLH-20(甲醇)柱色谱和反相 RP-18(甲醇-水:30%、50%、70%、90%)柱色谱由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)。化学结构式见图 1(Fig.1):

图 1 化合物 1～12的结构Fig.1 The structures of compounds 1-12

2 结构鉴定

Helioscopin D(1) C14H26O4,无色油状物,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)。计算其不饱和度为 2,从13C NMR谱可以看出,有 4个甲基,2个亚甲基,4个次甲基,3个季碳和 1个甲氧基,初步判断为一个降倍半萜,通过文献检索发现其结构与野鸦椿素B[1]相似,但是在 C-9的核磁数据有较小差异,所以推测是-OMe的连接位置不同所致。其平面结构通过HMBC图谱确定,HMBC图谱可以得出 H-12(δH0.86)与 C-1,C-2,C-6,C-11相关,H-11(δH1.18)与C-1,C-6,C-7,C-11相关,H-13(δH1.15)与 C-4/C-5/C-6相关,-OMe(δH3.31)与 C-9(δC79.9)相关,因此其平面结构得以鉴定。化合物 1的相对构型通过ROESY图谱确定,在 ROESY图谱中,可以看到信号 H-11与 H-3和 H-7相关,因此 OH-3和 OH-6均为β构型;当单照射 H-13时,发现 H-4,H-7,H-8信号增益,因此可以判断OH-5为α构型,这一判断通过与文献[2]比较得到进一步验证。H-7与 H-8的耦合常数为 15.9 Hz,表明双键为反式。侧链上 C-9的绝对构型尚未能测定。化合物 1为新化合物,命名为 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).主要二维相关如下图 2(Fig.2)。

图2 化合物1的主要HMBC和ROESY相关Fig.2 ROESY and HMBC correlations for compound 1

Isofraxidin(2) 白色固体。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)。以上数据与文献[3]数值相符。

Swertiamarin(3) 黄色油状物。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)。以上数据与文献[4]数值相符。

13-Carboxyblumenol C(4) 无色油状物。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),以上数据与文献[5]数值相符。

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),以上数据与文献[6]数值相符。

(+)-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)以上数据与文献[7]数值相符。

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) 无定形粉末。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),以上数据与文献[8]数值相符。

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),以上数据与文献[9]数值相符。

(6R,9S)-megastigman-3-one-4,7-ene-9-ol-9-O-α-L-arabinofuranosyl-(1→6)-β-D-glucopyranoside(9) 无色粉末。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),该化合物结构与文献[10]化合物相似,但首次归属了其核磁共振数据。

2R,3R-2,3-D ihydro-2-(4′-hydroxy-3′-methoxyphenyl)-3-(glucosyloxymethyl)-7-methoxybenzofuran-5-propanol(dihydrodehydrodicon iferylalcohol-β-D-glucoside)(10) 无色油状物。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),以上数据与文献[11]数值相符。

Thym idine(11) 淡黄色固体。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),以上数据与文献[12]数值相符。

Deoxyurid ine(12) 淡黄色固体。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),以上数据与文献[12]数值相符。

1 Zhang XB(张小波),Lin WH(林文翰),Deng Z W(邓志威),et al.Chemical constitutents from Chinese mangrove plant cerbera manghas.Chin Tradit Herb D rugs(中草药), 2006,10:1447-1449.

2 Yoshio T,Yoshiro O,Toshiya M,et al.New megastigmane and tetraketide from the leaves ofEuscaphis japonica.Chem Phar m Bull,2000,48:752-754.

3 Mayuree K,Nijisiri R,Toshiko W,et al.Chemical constituentsof pterocaulon redolens.Heterocycles,2003,61:183-187.

4 Wei G M,Nicola F,Jean CW,et al.Rhodenthoside A,a new type of acylated secoiridoid glycoside fromGentianrhodentha.Hel Chem Acta,1994,77:1660-1671.

5 Zhao AH(赵爱华),Peng LY(彭丽艳),Wang ZY(王宗玉),et al.An ionone derivative fromIsodon leucophyllus.Acta Botanica Yunnanica(云南植物研究),2003,25:503-506.

6 LiN(李宁),Tan NH(谭宁华),Zhou J(周俊).A new lignan glycoside fromCurculigo capitulate.Acta Botanica Yunnanica(云南植物研究),2003,25:711-715.

7 TakeshiD,Takako I,SanseiN.The constituentsof EucommiaulmoidesO liv.Ⅱ.Isolation and structures of three new lignan glycosides.Chem Phar m Bull,1985,33:3651-3657.

8 Akiyo S,MaksutC,SanseiN.Dihydrobenzofuran lignans fromBoreava orientalis.Phytochem istry,1996,43:1349-1354.

9 Lennart NL,Thomas P,Olof T.Diligol glycosides from needles ofPicea abies.Phytochem istry,1981,20:1967-1969.

10 W iyada K,HideakiO,Somsak R.Leeaoside,a new megastigmane diglycoside from the leaves ofLeeathorelii gagnep.J NatM ed,2007,61:449-451.

11 Beate B,Peter W.Isolation and characterization of novel benzotaes,cinnmaters,flavonoids,and lignans from Riesling wine and screening for antioxidant activity.J Agric Food Chem,2001,49:2788-2798.

12 Gong YH(龚运淮),Ding LS(丁立生).13C NMR Resonance ofNatural Products(天然产物核磁共振13C NMR碳谱分析).Kunming:Yunnan Science and Technology Press, 2005.943.

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”新药创制重大专项 (2008ZX09401-004);云南省中青年学术技术带头人基金 (2007PY01-48)

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