田巒鳶,陳家春,白 雪,方進(jìn)波

華中科技大學(xué)同濟醫(yī)學(xué)院藥學(xué)院天然藥物化學(xué)與資源評價湖北重點實驗室,武漢 430030

紫紅獐牙菜口山酮及環(huán)烯醚萜類化合物的研究

田巒鳶,陳家春＊,白 雪,方進(jìn)波

華中科技大學(xué)同濟醫(yī)學(xué)院藥學(xué)院天然藥物化學(xué)與資源評價湖北重點實驗室,武漢 430030

采用各種柱色譜法對紫紅獐牙菜的石油醚和正丁醇部位進(jìn)行分離純化,從石油醚部位分離鑒定得到 6個化合物,利用理化性質(zhì)和波譜學(xué)方法分別鑒定為 oleanolic acid(1),swerchirin(2),sweriaperenine(3),bellidifolin(4),gentiacaulein(5)和 1,7,8-trihydroxy-3-methoxyxanthone(6);從正丁醇部位分離鑒定得到 9個化合物,分別鑒定為 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首次從該屬植物中得到,化合物 9、10、12和13首次從該植物中分離得到。

紫紅獐牙菜;石油醚部位;正丁醇部位;口山酮;烯醚萜

紫紅獐牙菜 Swertia puniceaHemsl.為龍膽科(Gentianaceae)獐牙菜屬 (Swertia L.)植物,主要分布于湖北、四川及貴州等省,藥用全草,具有清利肝膽、清熱除濕的功效[1]?，F(xiàn)代藥理研究表明紫紅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,已報道紫紅獐牙菜主要有口山酮、三萜和環(huán)烯醚萜類等化學(xué)成分[4-12]。為了研究該藥用植物抗 HBV和降血糖的活性物質(zhì)基礎(chǔ),我們對其展開了進(jìn)一步的化學(xué)成分研究,前期已報道其乙酸乙酯部位和部分水溶性的化學(xué)成分[12],本實驗對該植物的石油醚部位和正丁醇部位進(jìn)行了系統(tǒng)分離,從中得到 15個化合物: 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首次從該屬植物中分離得到,化合物 9、10、12和 13首次從該植物分離得到。

1 儀器與材料

XT-4顯微熔點儀 (溫度未校正);Bruker AM-400型核磁共振儀(T MS為內(nèi)標(biāo));Brukermicro TOFQ型質(zhì)譜儀;Nicole NEXUS型傅立葉轉(zhuǎn)換紅外光譜儀;薄層色譜及柱色譜用硅膠 (中國青島海洋化工公司);TOYOPEARL HW-40(TOSOH公司);SephadexLH-20,ODS-A(50μm,Y MC公司)。標(biāo)準(zhǔn)品oleanolic acid(中國生物制品研究所,批號: 110742200314)。

藥材于 2005年 9月采自湖北省鶴峰縣,經(jīng)本文作者陳家春教授鑒定為 Swertia puniceaHemsl.,憑證標(biāo)本存放于華中科技大學(xué)同濟醫(yī)學(xué)院藥學(xué)院生藥學(xué)研究室。

2 提取與分離

3.6 kg干燥全草用 90%乙醇滲漉提取,提取液適當(dāng)濃縮后依次用石油醚、醋酸乙酯、正丁醇萃取。分別得到石油醚萃取物 172 g和正丁醇萃取物 119 g。取石油醚萃取物拌入 120 g硅膠,經(jīng)硅膠 (100～200目)柱層析,用石油醚-醋酸乙酯 (30∶1～2∶1)梯度洗脫得到 3個組分 P1-P3。組分 P1和 P2經(jīng)TOYOPEARL HW-40(氯仿-甲醇 2∶1)洗脫,再經(jīng)硅膠柱色譜(石油醚-醋酸乙酯 50∶1)洗脫分別得到化合物 1(1 g)、2(73 mg)和化合物 3(1.5 g)、4 (228 mg)、5(114 mg);組分 P3經(jīng)硅膠柱色譜 (石油醚-醋酸乙酯 15∶1)洗脫,再經(jīng) SephadexLH-20(甲醇)純化得到化合物 6(12 mg)。正丁醇萃取物拌入 125 g硅膠,經(jīng)(100～200目)硅膠柱層析用氯仿-甲醇 (8∶2,7∶3,6∶4,4∶6)梯度洗脫得到 5個組分B1-B5。組分 B1和 B2經(jīng) TOYOPEARL HW-40(氯仿-甲醇 2∶1)和硅膠柱色譜(氯仿-甲醇 9∶1-8∶2)洗脫,再用 SephadexLH-20(甲醇)純化分別得到化合物 7(78 mg),8(160 mg)和化合物 11(156 mg);組分B3經(jīng)硅膠柱色譜(氯仿-甲醇 5∶1)洗脫后得到 2個組分 B3-1和 B3-2,B3-1和 B3-2分別經(jīng) ODS-A (甲醇-水 1∶9)分離,再經(jīng) SephadexLH-20(甲醇)純化得到化合物 9(6 mg)、10(9 mg)和 12(16 mg),組分B4和組分B5經(jīng)硅膠柱色譜(氯仿-甲醇 4∶1)分離后用 SephadexLH-20(甲醇)純化分別得到化合物13(60 mg)、14(24 mg)和化合物 15(40 mg)。

3 結(jié)構(gòu)鑒定

化合物 1 白色針狀結(jié)晶。mp.307～309℃; I R、薄層 Rf值與標(biāo)準(zhǔn)品 oleanolic acid對照相一致。

化合物 2 黃色針晶。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)。以上數(shù)據(jù)與文獻(xiàn)[13]對照,確定化合物 2為 swerchirin。

化合物 3 黃色針晶。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)。以上數(shù)據(jù)與文獻(xiàn)[13]對照,確定化合物 3為 sweriaperenine。

化合物 4 黃色針狀結(jié)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)。以上數(shù)據(jù)與文獻(xiàn)[14]對照,確定化合物 4為 bellidifolin。

化合物 5 黃色針晶。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)。以上數(shù)據(jù)與文獻(xiàn)[13]對照,確定化合物 5為 gentiacaulein。

化合物 6 黃色針狀結(jié)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)。以上數(shù)據(jù)與文獻(xiàn)[15]對照,確定化合物 6為 1,7,8-trihydroxy-3-methoxyxanthone。

化合物 7 黃色無定形粉末。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,糖上質(zhì)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)。以上數(shù)據(jù)與文獻(xiàn)[16]對照,確定化合物 7為 8-[(β-D-glucopyranosyl)oxy]-1,5-dihydroxy-3-methoxyxanthone。

化合物 8 黃色無定形粉末。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(糖上質(zhì)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)。以上數(shù)據(jù)與文獻(xiàn)[16]對照,確定化合物 8為 5-[(β-D-glucopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone。

化合物 9 黃色無定形粉末。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,糖上質(zhì)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)。以上數(shù)據(jù)與文獻(xiàn)[17]對照,確定化合物 9為 7-[(β-D-xylopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone。

化合物 10 黃色無定形粉末。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,糖上質(zhì)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′)。以上數(shù)據(jù)與文獻(xiàn)[16]對照,確定化合物 10為 8-[(β-D-glucopyranosyl)oxy]-1,3,5-trimethoxyxanthone。

化合物 11 白色無定形粉末。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)。以上數(shù)據(jù)與文獻(xiàn)[18]對照,確定化合物 11為 swertiamarin。

化合物 12 淡黃色無定形粉末。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)。以上數(shù)據(jù)與文獻(xiàn)[19]對照,確定化合物 12為 tetrahydrosertianolin。

化合物 13 白色無定形粉末。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)。以上數(shù)據(jù)與文獻(xiàn)[20]對照,確定化合物 13為 8-hydroxy-10-hydrosweroside。

化合物 14 黃色無定形粉末。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)。以上數(shù)據(jù)與文獻(xiàn)[21]對照,確定化合物 14為 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′)。以上數(shù)據(jù)與文獻(xiàn)[22]對照,確定化合物 15為 uridine。

1 Wan DR(萬定容),Chen JC(陳家春),Yu HH(余漢華). Codex of HubeiMedicinaMaterials(湖北藥材志).Wuhan: Hubei Science and Technology Publishing Company,2002. 533.

2 Tian LY(田巒鳶),Hang FJ(黃鳳嬌),Zhang XQ(張秀橋).Inhibitory EthylAcetate Effectof the Extracts of Swertia Punicea Hemsl on Hepatitis B Virus in Vitro.J Hubei Coll Tradit Chin M ed(湖北中醫(yī)學(xué)院學(xué)報),2006,8:5-7.

3 WenL(文莉),Chen JC(陳家春).HypoglycemicActivityof S.punicea Hemal Extracts in Streptozotocin Induced Hyperglycemic Mice.China Phar m(中國藥師),2007,10:140-142.

4 Tan P(譚沛),Liu YL(劉永隆),Hou CY(侯翠英).Swertiapun imarin fromSwertia puniceaHemsl..Acta Phar m Sini-ca(藥學(xué)學(xué)報),1993,28:522-525.

5 Fukamiya N,OkanoM,Kondo K,et al.Xanthones fromSwertia punicea.J Natl Prod,1990,53:1543-1547.

6 Tan P,Hou CY,Liu YL,et al.Swertipunicoside.The first bisxanthone C-glycoside.J O rg Chem,1991,56:7130-7133.

7 Tan P(譚沛),Liu YL(劉永隆),Hou CY(侯翠英).Swertiapuniside fromSwertia puniceaHemsl..Acta Phar m Sinica (藥學(xué)學(xué)報),1992,27:476-479.

8 Tan P,Hou CY,Liu YL,et al.3-O-Demethylswertipunicoside fromSwertia punicea.Phytochem istry,1992,31:4313-4315.

9 Luo YH(羅躍華),Nie RL(聶瑞麟).The Secoiridoids Isolated fromSwertia punicea.Acta Bot Yunnan(云南植物研究),1993,15:97-100.

10 KanamoriH,Sakamoto I.The componentsofSwertia punicea. Hiroshima-ken Hoken Kankyo Senta Kenkyu Hokoku,1993, 1:13-16.

11 XinM,QiuMH,Nie RL,et al.A new monoterpene glycoside fromSwertia punicea.Chin Chem Lett,2000,11:709-710.

12 Zhang XQ(張秀橋),Tian LY(田巒鳶),Chen JC(陳家春),et al.Constituents fromSwertia puniceaHemsl..Chin Tradit Herb D rugs(中草藥),2007,38:1153-1154.

13 Hajimehdipour H,Amanzadeh Y,Ebrah imi SES,et al.Three Tetraoxygenated Xanthones fromSwertia longifolia.Phar m B iol,2003,41:497-99.

14 Bian QY(卞慶亞),Hou CY(侯翠英),Chen JM(陳建民). Chemical Constituents fromSwertia CalycinaFranch..Nat Prod Res Dev(天然產(chǎn)物研究與開發(fā)),1998,10:1-5.

15 JiLJ(紀(jì)蘭菊),Ding JY(丁經(jīng)業(yè)),Fan SF(樊淑芬),et al. Study on Chemical Constituents of GentianopsisBrabata var. Stennocalyx H.W.Li ex T.N.Ho.Acta Bot Sinica(植物學(xué)報),1992,34:203-207.

16 Zeng GY(曾光堯),Tan GS(譚桂山),Xu KP(徐康平),et al.Water-soluble Chemical Constituents ofSwertia davidi Franch..Acta Phar m Sinica(藥學(xué)學(xué)報),2004,39:351-353.

17 Sun HF(孫洪發(fā)),Hu BL(胡伯林),Ding JY(丁經(jīng)業(yè)),et al.The Glucosides fromSwertia M ussotiiFranch..Acta Bot Sinica(植物學(xué)報),1991,33:31-37

18 Luo YH(羅躍華),Nie RL(聶瑞麟).Studies on Iridoid Glucosides fromSwertia angustifolia.Acta Phar m Sinica(藥學(xué)學(xué)報),l992,27:l25-l29.

19 Koji H,Shigetoshi K,Purusotam B,et al.Tetrahydros wertianolin:a potent hepatoprotective agent fromSwertia japonica Makino.Chem Phar m Bull,1997,45:567-569.

20 Tan RX,Kong LD,Wei HX.Secoiridoid glycosides and an antifungal anthranilate derivative fromGentiana tibetica.Phytochem istry,1998,47:1223-1226.

21 Teodora J,Dijana K,Ivana A,et al.Xanthones and C-glucosides from the aerial parts of four species of Gentianella from Serbia and Montenegro.B iochem Syst Ecol,2005,33:729-735.

22 Yu DQ(于德泉),Yang JS(楊峻山).Analytic Chemistry Handbook.2nd Ed.7th Subolume.(分析化學(xué)手冊,第二版,第七分冊).Beijin:Chemical Industry Press,1999:907.

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

國家自然科學(xué)基金(30271590)

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

R284.1;Q946.91

A