紫红獐牙菜口山酮及环烯醚萜类化合物的研究

田峦鸢,陈家春,白 雪,方进波

华中科技大学同济医学院药学院天然药物化学与资源评价湖北重点实验室,武汉 430030

紫红獐牙菜口山酮及环烯醚萜类化合物的研究

田峦鸢,陈家春＊,白 雪,方进波

华中科技大学同济医学院药学院天然药物化学与资源评价湖北重点实验室,武汉 430030

采用各种柱色谱法对紫红獐牙菜的石油醚和正丁醇部位进行分离纯化,从石油醚部位分离鉴定得到 6个化合物,利用理化性质和波谱学方法分别鉴定为 oleanolic acid(1),swerchirin(2),sweriaperenine(3),bellidifolin(4),gentiacaulein(5)和 1,7,8-trihydroxy-3-methoxyxanthone(6);从正丁醇部位分离鉴定得到 9个化合物,分别鉴定为 8-[(β-D-glucopyranosyl)oxy]-1,5-dihydroxy-3-methoxyxanthone(7),5-[(β-D-glucopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone(8),7-[(β-D-xylopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone(9),8-[(β-D-glucopyranosyl)oxy]-1,3,5-trimethoxyxanthone(10),s wertiamarin(11),tetrahydrosertianolin(12),8-hydroxy-10-hydros weroside(13),campestroside(14)以及 uridine(15)。其中,化合物 15首次从该属植物中得到,化合物 9、10、12和13首次从该植物中分离得到。

紫红獐牙菜;石油醚部位;正丁醇部位;口山酮;烯醚萜

紫红獐牙菜 Swertia puniceaHemsl.为龙胆科(Gentianaceae)獐牙菜属 (Swertia L.)植物,主要分布于湖北、四川及贵州等省,药用全草,具有清利肝胆、清热除湿的功效[1]。现代药理研究表明紫红獐牙菜具有抗乙型肝炎病毒 (HBV)活性和降低 STZ糖尿病小鼠血糖的作用[2,3]。目前,已报道紫红獐牙菜主要有口山酮、三萜和环烯醚萜类等化学成分[4-12]。为了研究该药用植物抗 HBV和降血糖的活性物质基础,我们对其展开了进一步的化学成分研究,前期已报道其乙酸乙酯部位和部分水溶性的化学成分[12],本实验对该植物的石油醚部位和正丁醇部位进行了系统分离,从中得到 15个化合物: oleanolic acid(1),swerchirin (2),sweriaperenine (3),bellidifolin(4),gentiacaulein(5),1,7,8-trihydroxy-3-methoxyxanthone(6),8-[(β-D-glucopyranosyl)oxy]-1,5-dihydroxy-3-methoxyxanthone(7),5-[(β-D-glucopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone(8),7-[(β-D-xylopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone(9),8-[(β-D-glucopyranosyl)oxy]-1,3,5-trimethoxyxanthone(10),swertiamarin(11),tetrahydrosertianolin(12),8-hydroxy-10-hydros weroside(13),campestroside(14)和 uridine (15)。其中化合物 14和 15首次从该属植物中分离得到,化合物 9、10、12和 13首次从该植物分离得到。

1 仪器与材料

XT-4显微熔点仪 (温度未校正);Bruker AM-400型核磁共振仪(T MS为内标);Brukermicro TOFQ型质谱仪;Nicole NEXUS型傅立叶转换红外光谱仪;薄层色谱及柱色谱用硅胶 (中国青岛海洋化工公司);TOYOPEARL HW-40(TOSOH公司);SephadexLH-20,ODS-A(50μm,Y MC公司)。标准品oleanolic acid(中国生物制品研究所,批号: 110742200314)。

药材于 2005年 9月采自湖北省鹤峰县,经本文作者陈家春教授鉴定为 Swertia puniceaHemsl.,凭证标本存放于华中科技大学同济医学院药学院生药学研究室。

2 提取与分离

3.6 kg干燥全草用 90%乙醇渗漉提取,提取液适当浓缩后依次用石油醚、醋酸乙酯、正丁醇萃取。分别得到石油醚萃取物 172 g和正丁醇萃取物 119 g。取石油醚萃取物拌入 120 g硅胶,经硅胶 (100～200目)柱层析,用石油醚-醋酸乙酯 (30∶1～2∶1)梯度洗脱得到 3个组分 P1-P3。组分 P1和 P2经TOYOPEARL HW-40(氯仿-甲醇 2∶1)洗脱,再经硅胶柱色谱(石油醚-醋酸乙酯 50∶1)洗脱分别得到化合物 1(1 g)、2(73 mg)和化合物 3(1.5 g)、4 (228 mg)、5(114 mg);组分 P3经硅胶柱色谱 (石油醚-醋酸乙酯 15∶1)洗脱,再经 SephadexLH-20(甲醇)纯化得到化合物 6(12 mg)。正丁醇萃取物拌入 125 g硅胶,经(100～200目)硅胶柱层析用氯仿-甲醇 (8∶2,7∶3,6∶4,4∶6)梯度洗脱得到 5个组分B1-B5。组分 B1和 B2经 TOYOPEARL HW-40(氯仿-甲醇 2∶1)和硅胶柱色谱(氯仿-甲醇 9∶1-8∶2)洗脱,再用 SephadexLH-20(甲醇)纯化分别得到化合物 7(78 mg),8(160 mg)和化合物 11(156 mg);组分B3经硅胶柱色谱(氯仿-甲醇 5∶1)洗脱后得到 2个组分 B3-1和 B3-2,B3-1和 B3-2分别经 ODS-A (甲醇-水 1∶9)分离,再经 SephadexLH-20(甲醇)纯化得到化合物 9(6 mg)、10(9 mg)和 12(16 mg),组分B4和组分B5经硅胶柱色谱(氯仿-甲醇 4∶1)分离后用 SephadexLH-20(甲醇)纯化分别得到化合物13(60 mg)、14(24 mg)和化合物 15(40 mg)。

3 结构鉴定

化合物 1 白色针状结晶。mp.307～309℃; I R、薄层 Rf值与标准品 oleanolic acid对照相一致。

化合物 2 黄色针晶。mp.185～187℃;ESIMSm/z287[M-H]-;1H NMR(CD3OD,400MHz)δ: 11.94、11.83(each 1H,s,1,8-OH)7.24(1H,d,J= 9.2 Hz,H-6),6.72(1H,d,J=9.2 Hz,H-7),6.55 (1H,d,J=2.4 Hz,H-4),6.36(1H,d,J=2.4 Hz,H-2),3.96(3H,s,OCH3-3),3.90(3H,s,OCH3-5);13C NMR(CD3OD,100 MHz):184.6(C=O),167.5(C-3),162.9(C-1),157.8(C-4a),154.4(C-8),145.5 (C-4b),139.9(C-5),120.5(C-6),109.3(C-8a), 108.2(C-7),102.9(C-8b),97.9(C-2),93.2(C-4), 57.4(OCH3-3),56.0(OCH3-5)。以上数据与文献[13]对照,确定化合物 2为 swerchirin。

化合物 3 黄色针晶。mp.186～188℃;ESIMSm/z287[M-H]-;1H NMR(DMSO-d6,400 MHz) δ:11.94,11.83(each 1H,s,1,8-OH),7.40(1H,d,J =9.0 Hz,H-6),6.91(1H,d,J=9.0 Hz,H-5),6.48 (1H,d,J=2.0 Hz,H-4),6.33(1H,d,J=2.0 Hz,H-2),3.91(3H,s,OCH3-3),3.90(3H,s,OCH3-7);13C NMR(DMSO-d6,100 MHz)δ:184.3(C=O),167.0 (C-3),162.0(C-1),157.5(C-4a),149.3(C-4b), 148.8(C-8),142.3(C-7),120.8(C-6),107.0(C-8a),105.3(C-5),101.5(C-8b),96.9(C-2),92.4 (C-4)56.4(OCH3-6),55.7(OCH3-2)。以上数据与文献[13]对照,确定化合物 3为 sweriaperenine。

化合物 4 黄色针状结晶 (甲醇),mp.262～265℃;ESI-MSm/z:273[M-H]-;1H NMR(DMSO-d6,400 MHz)δ:11.911,11.078,9.722(each 1H,s, 1,8,5-OH),7.261(1H,d,J=9.0 Hz,H-6),6.655 (1H,d,J=9.0 Hz,H-7),6.641(1H,d,J=2.5 Hz, H-4),6.396(1H,d,J=2.5 Hz,H-2),3.901(3H,s, OCH3-3);13C NMR(DMSO-d6,100 MHz)δ:185.9(C =O),168.7(C-3),163.9(C-1),158.8(C-4a), 154.2(C-8),144.6(C-4b),138.1(C-5),124.9(C-6),110.1(C-7),108.5(C-8a),103.3(C-8b),98.3 (C-2),93.7(C-4),56.7(OCH3-3)。以上数据与文献[14]对照,确定化合物 4为 bellidifolin。

化合物 5 黄色针晶。mp.193～194℃;ESIMSm/z287[M-H]-;1H NMR(DMSO-d6,400 MHz) δ:13.28,8.32(each 1H,s,1,7-OH),7.41(1H,d,J =9.2 Hz,H-6),7.21(1H,d,J=9.2 Hz,H-5),6.45 (1H,d,J=2.4 Hz,H-4),6.29(1H,d,J=2.4 Hz,H-2),3.91(3H,s,OCH3-3),3.90(3H,s,OCH3-8);13C NMR(DMSO-d6,100 MHz)δ:181.7(C=O),167.6 (C-3),164.6(C-1),158.2(C-4a),151.2(C-8), 147.8(C-4b),146.2(C-7),124.6(C-6),116.0(C-8a),114.6(C-5),104.6(C-8b),97.6(C-2),92.5 (C-4),62.3(OCH3-6),56.4(OCH3-1)。以上数据与文献[13]对照,确定化合物 5为 gentiacaulein。

化合物 6 黄色针状结晶 (乙醇)。mp.206～208℃;ESI-MSm/z273[M-H]-;1H NMR(DMSO-d6,400 MHz)δ:11.89,11.63,9.43(each 1H,s,1,8, 7-OH),7.29(1H,d,J=9.0 HZ,H-6),6.90(1H,d,J =9.0 Hz,H-5),6.60(1H,d,J=2.5 Hz,H-4),6.39 (1H,d,J=2.5 Hz,H-2),3.876(3H,s,OCH3-3)。13C NMR(DMSO-d6,100 MHz)δ:184.3(C=O), 167.1(C-3),161.9(C-1),157.7(C-4a),148.0(C-4b),147.0(C-8),140.6(C-7),124.2(C-6),107.4 (C-8a),106.1(C-5),101.9(C-8b),97.25(C-2), 92.8(C-4),56.3(OCH3-3)。以上数据与文献[15]对照,确定化合物 6为 1,7,8-trihydroxy-3-methoxyxanthone。

化合物 7 黄色无定形粉末。ESI-MSm/z435 [M-H]-;1H NMR(DMSO-d6,400 MHz)δ:13.09, 10.06(each 1H,s,1,5-OH),7.27(1H,d,J=8.4 Hz,H-6),7.13(1H,d,J=8.4 Hz,H-7),6.58(1H, d,J=2.0 Hz,H-4),6.37(1H,d,J=2.0 Hz,H-2), 4.82(1H,d,J=8.0 Hz,H-1′),3.20～3.73(m,糖上质子),3.89(3H,s,OCH3-3);13C NMR(DMSO-d6, 100 MHz)δ:181.8(C=O),167.0(C-3),163.4(C-1),157.1(C-4a),150.2(C-8),145.8(C-4b),141.7 (C-5),121.8(C-6),113.2(C-7),112.7(C-8a), 104.3(C-1′),103.9(C-8b),97.9(C-2),92.9(C-4),78.2(C-5′),76.8(C-3′),74.2(C-2′),70.5(C-4′),61.6(C-6′),56.6(OCH3-3)。以上数据与文献[16]对照,确定化合物 7为 8-[(β-D-glucopyranosyl)oxy]-1,5-dihydroxy-3-methoxyxanthone。

化合物 8 黄色无定形粉末。ESI-MSm/z435 [M-H]-;1H NMR(DMSO-d6,400 MHz)δ:11.81、11.37(each 1H,s,1,8-OH),7.62(1H,d,J=9.0 Hz,H-6),6.73(1H,d,J=9.0 Hz,H-7),6.68(1H, d,J=2.0 Hz,H-4),6.42(1H,d,J=2.0 Hz,H-2), 4.6-3.674(糖上质子),4.90(1H,d,J=8.0 Hz,H-1′),3.90(3H,s,OCH3-3);13C NMR(DMSO-d6,100 MHz)δ:183.8(C=O),167.2(C-3),161.8(C-1), 157.4(C-4a),150.2(C-8),145.4(C-4b),137.3(C-5),125.8(C-6),109.4(C-7),107.5(C-8a),102.3 (C-1′),102.1(C-8b),97.8(C-2),93.3(C-4),77.2 (C-5′),76.5(C-3′),73.4(C-2′),69.7(C-4′),61.6 (C-6′),56.6(OCH3-3)。以上数据与文献[16]对照,确定化合物 8为 5-[(β-D-glucopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone。

化合物 9 黄色无定形粉末。ESI-MSm/z435 [M-H]-;1H NMR(CD3OD,400 MHz)δ:7.58(1H,d, J=9.2 Hz,H-6),6.85(1H,d,J=9.2 Hz,H-5), 6.47(1H,d,J=2.4 Hz,H-4),6.31(1H,d,J=2.4 Hz,H-2),5.07(1H,d,J=7.6 Hz,H-1′),4.37-3.30 (m,糖上质子),3.88(3H,s,-OCH3);13C NMR (CD3OD,100 MHz)δ:183.2(C=O),166.3(C-3), 161.1(C-1),156.5(C-4a),149.7(C-4b),149.2(C-8),104.1(C-5),125.4(C-6),137.9(C-7),106.5 (C-8a),100.3(C-1′),99.5(C-8b),98.7(C-2), 90.9(C-4),76.4(C-5′),75.8(C-3′),72.1(C-2′), 68.5(C-4′),59.8(C-6′),54.8(OCH3-3)。以上数据与文献[17]对照,确定化合物 9为 7-[(β-D-xylopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone。

化合物 10 黄色无定形粉末。ESI-MSm/z 421[M-H]-;1H NMR(CD3OD,400 MHz)δ:6.97 (1H,d,J=8.8 Hz,H-7),6.92(1H,d,J=8.8 Hz,H-6),6.15(1H,d,J=2.4 Hz,H-4),5.91(1H,d,J= 2.4 Hz,H-2),4.49(1H,d,J=7.6 Hz,H-1′),3.15～3.67(m,糖上质子);13C NMR(CD3OD,100 MHz) δ:180.2(C=O),164.8(C-3),162.3(C-1),155.7 (C-4a),149.0(C-8),144.3(C-4b),140.2(C-5), 119.9(C-6),112.1(C-7),111.0(C-8a),103.0(C-1′),101.7(C-8b),97.6(C-2),92.2(C-4),75.8(C-5′),74.5(C-3′),72.1(C-2′),68.5(C-4′),59.8(C-6′)。以上数据与文献[16]对照,确定化合物 10为 8-[(β-D-glucopyranosyl)oxy]-1,3,5-trimethoxyxanthone。

化合物 11 白色无定形粉末。ESI-MSm/z397 [M+Na]+;UV(MeOH)λmax nm:234。1H NMR (C5D5N,400 MHz)δ:7.95(1H,s,H-3),5.96(1H,br s,H-1),5.29(1H,d,J=7.8 Hz,H-1′),5.06～5.37 (3H,m,H-8、10),3.02(1H,d,J=9.8 Hz,H-9), 1.77～1.79(2H,m,H-6);13C NMR(C5D5N,100 MHz)δ:163.836(C=O),151.054(C-3),131.524 (C-8),119.330(C-10),108.516(C-4),97.733(C-1′),96.241(C-1),78.085(C-5′),77.234(C-3′), 73.420(C-2′),70.052(C-4′),63.339(C-7),62.854 (C-5),61.180(C-6′),49.527(C-9),31.588(C-6)。以上数据与文献[18]对照,确定化合物 11为 swertiamarin。

化合物 12 淡黄色无定形粉末。ESI-MSm/z 439[M-H]-;1H NMR(CD3OD,400 MHz)δ:6.57 (1H,d,J=4.0 Hz,H-4),6.36(1H,d,J=4.0 Hz,H-2),4.99(1H,t,J=4.0 Hz,H-8),4.73(1H,d,J= 8.0 Hz,H-1′),4.65(1H,dd,J=9.6,7.2 Hz,H-5), 3.92(1H,dd,J=12.0,2.4 Hz,Hb-6′),3.89(3H,s, OCH3-3),3.75(1H,dd,J=12.0,4.0 Hz,Ha-6′), 3.42(1H,t,J=8.8 Hz,H-3′),3.35(1H,m,H-5′), 3.30(1H,m,H-4′),3.17(1H,dd,J=8.8,8.0 Hz, H-2′),2.33(1H,dq,J=12.0,4.0 Hz,Heq-7),2.13 (2H,m,H-6),1.81(1H,tt,J=12.0,4.0 Hz,Hax-7);13C NMR(CD3OD,100 MHz)δ:180.2(C=O), 165.7(C-4b),164.6(C-3),160.3(C-1),156.2(C-4a),115.2(C-8a),103.3(C-8b),102.3(C-1′), 96.2(C-2),90.5(C-4),75.2(C-5′),75.0(C-3′), 72.8(C-2′),68.6(C-4′),68.1(C-8),64.6(C-5), 60.0(C-6′),53.6(C-OCH3),25.1(C-7),24.5(C-6)。以上数据与文献[19]对照,确定化合物 12为 tetrahydrosertianolin。

化合物 13 白色无定形粉末。ESI-MSm/z399 [M+Na]+;1H NMR(CD3OD,400 MHz)δ:7.61 (1H,d,J=2.4 Hz,H-3),5.93(1H,d,J=1.6 Hz,H-1),4.69(1H,d,J=8.0 Hz,H-1′),4.37(1H,m,H-7a),4.23(1H,m,H-7b),3.91(1H,dd,J=12.0,2.0 Hz,H-6′a),3.68(1H,dd,J=12.0,4.0 Hz,H-6′b),3.47(1H,dd,J=8.0,9.0 Hz,H-2′),3.42(1H, m,H-3′),3.37(1H,m,H-4′),3.23(1H,dd,J= 6.0,6.4 Hz,H-8),3.17(1H,m,H-5′),3.07(1H, m,H-5),2.02(1H,m,H-6a),1.99(1H,m,H-9), 1.89(1H,m,H-6b),1.32(1H,d,J=6.4 Hz,H-10);13C NMR(CD3OD,100MHz)δ:165.8(C=O), 151.9(C-3),103.6(C-4),97.0(C-1′),92.9(C-1), 75.5(C-3′),75.2(C-5′),72.0(C-2′),68.7(C-4′), 67.2(C-8),62.3(C-7),60.1(C-6′),41.6(C-9), 25.8(C-5),23.4(C-6),21.3(C-10)。以上数据与文献[20]对照,确定化合物 13为 8-hydroxy-10-hydrosweroside。

化合物 14 黄色无定形粉末。ESI-MSm/z425 [M-H]-,1H NMR(CD3OD,400 MHz)δ:6.57(1H, d,J=2.0 Hz,H-4),6.36(1H,d,J=2.0 Hz,H-2), 4.99(1H,t,J=2.8 Hz,H-8),4.73(1H,d,J=8.0 Hz,H-1′),4.64(1H,dd,J=9.6,2.4 Hz,H-5),3.90 (1H,dd,J=12.0,2.0 Hz,Ha-6′),3.75(1H,dd,J =12.0,5.2 Hz,Hb-6′),3.43～3.35(2H,m,H-3′、H-5′),3.31(1H,m,H-4′),3.16(1H,dd,J=1.2, 8.0 Hz,H-2′),2.33(1H,brd,J=14.4 Hz,Heq-7), 2.13(2H,m,H-6),1.81(1H,tt,J=14.4,3.2 Hz, Hax-7);13C NMR(CD3OD,100 MHz)δ:180.0(C= O),165.4(C-4b),163.3(C-3),160.5(C-1),156.4 (C-4a),114.9(C-8a),102.5(C-8b),102.3(C-1′), 97.2(C-2),92.1(C-4),75.3(C-5′),75.0(C-3′), 72.8(C-2′),68.6(C-4′),68.3(C-8),64.6(C-5), 59.9(C-6′),25.0(C-7),24.5(C-6)。以上数据与文献[21]对照,确定化合物 14为 campestroside。

化合物 15 白色粉末。ESI-MSm/z243[MH]-;1H NMR(CD3OD,400 MHz)δ:6.72(1H,d,J= 8.0 Hz,H-6),4.62(1H,d,J=4.8 Hz,H-1′),4.42 (1H,d,J=8.0 Hz,H-5),2.92-2.86(2H,m,H-3′, 4′),2.73(1H,m,H-2′),2.56(1H,dd,J=12.4,2.8 Hz,H-5),2.451(H,dd,J=12.4,2.8 Hz,H-5);13C NMR(CD3OD,100 MHz)δ:163.3(C-4),149.6(C-2),139.8(C-6),99.8(C-5),87.8(C-1′),83.4(C-4′),72.8(C-2′),68.4(C-3′),59.4(C-5′)。以上数据与文献[22]对照,确定化合物 15为 uridine。

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Xanthonoids and Iridoid Glycosides fromSwertia puniceaHem sl.

TIAN Luan-yuan,CHEN Jia-chun＊,BA IXue,FANG Jin-bo
Hubei Key Laboratory of NaturalM edicinal Chem istry and Resource Evaluation,Tongji School of Phar maceutical Sciences,Huazhong University of Science and Technology,W uhan 430030,China

The chemical constituents ofSwertia puniceaHemsl.were isolated by various column chromatographic methods.Fifteen compoundswere obtained and identified as oleanolic acid(1),swerchirin(2),s weriaperenine(3),bellidifolin(4),gentiacaulein(5),isobellidifolin(6),8-[(β-D-glucopyranosyl)oxy]-1,5-dihydroxy-3-methoxyxanthone(7), 5-[(β-D-glucopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone(8),7-[(β-D-xylopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone(9),8-[(β-D-glucopyranosyl)oxy]-1,3,5-trimethoxyxanthone(10),swertiamarin(11),tetrahydrosertianolin(12),8-hydroxy-10-hydros weroside(13),campestroside(14),and uridine(15).Compounds 15 were isolated from this genus and 9,10,12,13 were obtained from this plant for the first time.

Swertia puniceaHemsl.;petroleum ether fraction;n-butanol fraction;xanthonoids;iridoid glycosides

1001-6880(2010)06-0979-05

2009-02-24 接受日期:2009-04-10

国家自然科学基金(30271590)

＊通讯作者 Tel:86-27-83692482;E-mail:homespringchen@126.com

R284.1;Q946.91

A