紫紅獐牙菜口山酮及環烯醚萜類化合物的研究

田巒鳶,陳家春,白 雪,方進波

華中科技大學同濟醫學院藥學院天然藥物化學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烯醚萜類化合物的研究

田巒鳶,陳家春＊,白 雪,方進波

華中科技大學同濟醫學院藥學院天然藥物化學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,利用理化性質和波譜學方法分別鑒定為 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]。現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、三萜和環烯醚萜類等化學成分[4-12]。為了研究該藥用植物抗 HBV和降血糖的活性物質基礎,我們對其展開了進一步的化學成分研究,前期已報道其乙酸乙酯部位和部分水溶性的化學成分[12],本實驗對該植物的石油醚部位和正丁醇部位進行了系統分離,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為內標);Brukermicro TOFQ型質譜儀;Nicole NEXUS型傅立葉轉換紅外光譜儀;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)。標準品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,經本文作者陳家春教授鑒定為 Swertia puniceaHemsl.,憑證標本存放于華中科技大學同濟醫學院藥學院生藥學研究室。

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TOYOPEARL HW-40(氯仿-甲醇 2∶1)洗脫,再經硅膠柱色譜(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經硅膠柱色譜 (石油醚-醋酸乙酯 15∶1)洗脫,再經 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(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 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 ODS-A (甲醇-水 1∶9)分離,再經 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 結構鑒定

化合物 1 白色針狀結晶。mp.307～309℃; I R、薄層 Rf值與標準品 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)。以上數據與文獻[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)。以上數據與文獻[13]對照,確定化合物 3為 sweriaperenine。

化合物 4 黃色針狀結晶 (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)。以上數據與文獻[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)。以上數據與文獻[13]對照,確定化合物 5為 gentiacaulein。

化合物 6 黃色針狀結晶 (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)。以上數據與文獻[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)。以上數據與文獻[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)。以上數據與文獻[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)。以上數據與文獻[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′)。以上數據與文獻[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)。以上數據與文獻[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)。以上數據與文獻[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)。以上數據與文獻[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)。以上數據與文獻[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′)。以上數據與文獻[22]對照,確定化合物 15為 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

國家自然科學基金(30271590)

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

R284.1;Q946.91

A