药食两用植物刺梨的化学成分研究
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药食两用植物刺梨的化学成分研究
综合应用天然产物化学分离、纯化技术从药食两用植物刺梨中分离得到13个化合物,结合各单体化合物的理化性质和光谱数据鉴定其结构。
依次为2-oxo-pomolic acid(1),1-β-羟基蔷薇酸(2),蔷薇酸(3),arjunic acid(4),委陵菜酸(5),刺梨苷(6),野蔷薇苷(7),arjunetin(8),2α,3α,19α-trihydroxy-olean-12-en-28-oic acid 28-O-β-D-glucopyranoside(9),2α,3α,19α,24-tetrahydroxyolean-12-en-28-oic-acid 28-O-β-D-glucopyranosyl ester(10),焦性没食子酸(11),β-胡萝卜苷(12),1,2-癸二醇(13)。
化合物9,10为首次从蔷薇科植物中分离得到,化合物1,4,5,9~11,13为首次从该植物中分离得到。
标签:刺梨;药食两用植物;化学成分
[Abstract]Rosa roxburghii,a kind of the medical and edible plants belonging to the Rosaceae family,is widely distributed in the southwest districts of China,especially Guizhou province. Now,by reason of the extensive bioactivities,the plant is widely used in the field of food,health product,drug,and so on. In the course of our continuing search for the bioactive constituents,thirteen compounds were isolated from R. roxburghii,and their structures were determined on the basis of physicochemical property,spectroscopic data and comparison with the literatures,as 2-oxo pomolic acid(1),1β-hydroxyeuscaphic acid(2),euscaphic acid(3),arjunic acid(4),tormentic acid(5),kaiiichigeside F1(6),rosamultin (7),arjunetin(8),2ɑ,3ɑ,19ɑ-trihydroxy-olean-12-en-28-oic acid 28-O-β-D-glucopyranoside(9),2α,3α,19α,24-tetrahydroxyolean-12-en-28-oic-acid 28-O-β-D-glucopyranosyl ester(10),pyrogallic acid (11),daucosterol(12),and 1,2-decanediol(13). Compounds 9 and 10 were firstly obtained from Rosaceae family,and compounds 1,4,5,9-11,13 were isolated from this plant for the first time.
[Key words]Rosa roxburghii;medical and edible plants;chemical constituents
刺梨为蔷薇科植物缫丝花Rosa roxburghii Tratt的果实,广泛分布于暖温带及亚热带地区,我国主要分布在西南三省,尤以贵州资源最为丰富,是贵州特色水果资源,具有“维C之王”的美誉[1-2]。
具有消食健脾,收敛止泻的功效,主要用于治疗积食腹胀、泄泻、止痛等疾病[3];现代研究发现其主要含有五环三萜和黄酮类物质,在增强免疫力、抗动脉粥样硬化、延缓衰老、抗癌防癌抗突变、健胃消食等方面均具有较好的辅助作用[4-8]。
作为药食两用植物先后收录于卫生部食品新资源品种(2004年17号公告)和《贵州省中药材、民族药材质量标准》(1994,2003年版),目前贵州省作为区域重点药食两用植物资源进行大力研发,正广泛应用于食品、保健食品、医药领域[3]。
为了进一步明确刺梨的化学物质基础,本文从刺梨中分离到10个五环三萜(1~10),其中化合物9,10为首次从蔷薇科植物中分离得到,化合物1,4~5,9~11,13为首次从该植物中分离
得到。
1材料
INOV A 400 MHz核磁共振测试仪(TMS内标)(Varian,Inc),INOV A 400 MHz 核磁共振测试仪(TMS内标)(Varian,Inc),国产500 MHz液体核磁共振谱仪(中国科学院武汉物理数学研究所);HP-5793气相色谱-质谱联用仪(美国惠普公司);Agilent 1100 HPLC-MSD型液相色谱-质谱联用仪(美国惠普公司);柱色谱硅胶(40~80,300~400目,青岛海洋化工有限公司);Sephadex LH-20(25~100 μm)(Amersham Biosciences,Sweden);半制备HPLC Waters 2489(UV/Visible Detector,Waters 600 Controller,美国Waters公司),半制备色谱柱为SunFireTM-C18(Waters,10 μm,10 mm×150 mm),分离纯化用试剂均由工业纯重蒸处理后使用。
药材采自贵州龙里县,经贵州大学安华明教授鉴定为蔷薇科植物缫丝花R. roxburghii 的果实(刺梨,栽培种),标本存于贵州省中国科学院天然产物化学重点实验室(编号GZNPC2014-03)。
2提取与分离
新鲜刺梨(10 kg)洗净、切碎后,用95%乙醇回流提取3次,每次2~3 h,合并提取液,减压浓缩至无醇味后加适量蒸馏水分散,依次用石油醚、乙酸乙酯、正丁醇萃取,萃取液减压浓缩得石油醚萃取物(59 g)、乙酸乙酯萃取物(328 g)、正丁醇萃取萃取物(183 g)、水层浸膏(1 627 g)。
乙酸乙酯萃取部分经硅胶柱色谱石油醚-丙酮(50∶1~0∶1)进行梯度洗脱,经TLC检测合并相同组分到7个流分(A 1~A 7)。
A 3流分(石油醚-丙酮,10∶1)经过硅胶柱色谱以石油醚-乙酸乙酯(20∶1~0∶1)梯度洗脱得到5个亚流分(A 3.1~A 3.5), A 3.2流分减压回收溶剂后经甲醇重结晶得到11(77 mg),A 3.3经Sephadex LH-20凝胶柱色谱氯仿-甲醇(1∶1)洗脱后合并相同组分减压回收溶剂得13(49 mg)。
A 5流分(石油醚-丙酮,5∶1)经硅胶柱色谱石油醚-丙酮(8∶1)洗脱后再经Sephadex LH-20凝胶柱色谱甲醇洗脱除杂,合并相同组分减压回收溶剂后经甲醇重结晶得到化合物1(19 mg)。
A 6流分(石油醚-丙酮,3∶1)经硅胶柱色谱石油醚-丙酮(15∶1~0∶1)梯度洗脱得4个亚流分(A 6.1~A 6.4);A 6.1流分减压回收溶剂后得12(109 mg);A 6.2流分经硅胶柱色谱石油醚-丙酮(7∶1)洗脱后经TLC检测合并相同组分得3(26 mg),4(31 mg),5(18 mg);A 6.3流分经Sephadex LH-20凝胶柱色谱甲醇洗脱后经甲醇重结晶得到化合物2(52 mg)。
正丁醇萃取部分经硅胶柱色谱氯仿-甲醇(20∶1~0∶1)进行梯度洗脱,经TLC检测合并相同组分到6个流分(B 1~B 6)。
B 2流分经硅胶柱色谱氯仿-甲醇(10∶1~3∶1)梯度洗脱得3个亚流分(B 2.1~B 2.3),B 2.1减压回收溶剂经甲醇重结晶得6(207 mg);B 3流分经Sephadex LH-20凝胶柱色谱甲醇洗脱除杂,合并相同组分减压回收溶剂后经甲醇重结晶得到化合物7(72 mg)。
B 5流分经硅胶柱色谱氯仿-甲醇(10∶1~0∶1)梯度洗脱得5个亚流分(B 5.1~B 5.5),B 5.1减压回收溶剂经甲醇重结晶得8(25 mg);B 5.3流分经Sephadex LH-20
凝胶柱色谱甲醇洗脱除杂后,经半制备HPLC(甲醇-水51∶49)进行分离纯化,分别得9(19 mg),10(31 mg)。
3结构鉴定
化合物1白色粉末(甲醇);EI-MS m/z 487 [M+H]+;1H-NMR(CD3OD,400 MHz)δ:5.28(1H,br s,H-12),3.98(1H,s,H-3),2.50(1H,s,H-18),1.39(3H,s,CH3-27),1.18(3H,s,CH3-29),1.17(3H,s,CH3-23),0.92(3H,d,J=9.2 Hz,CH3-30),0.89(3H,s,CH3-25),0.79(3H,s,CH3-26),0.71(3H,s,CH3-24);13C-NMR(CD3OD,100 MHz)δ:54.4(C-1),212.7(C-2),83.9(C-3),46.5(C-4),55.8(C-5),19.9(C-6),33.8(C-7),
41.4(C-8),48.2(C-9),44.5(C-10),24.5(C-11),128.7(C-12),140.1(C-13),
42.7(C-14),29.6(C-15),26.5(C-16),48.3(C-17),55.0(C-18),73.5(C-19),
43.0(C-20),27.3(C-21),38.4(C-22),29.6(C-23),17.2(C-24),17.1(C-25),16.6(C-26),24.7(C-27),182.2(C-28),27.0(C-29),16.6(C-30)。
以上数据与文献[9]报道基本一致,故鉴定化合物1为3β,19α-二羟基-2-氧-乌苏-12-烯-28-酸(2-oxo pomolic acid)。
化合物2白色粉末(甲醇);EI-MS m/z 505 [M+H]+;1H-NMR(CD3OD,500 MHz)δ:5.28(1H,br s,H-12),3.65(1H,dd,J=9.6,2.8 Hz,H-2),3.45(1H,d,J=9.6 Hz,H-1),3.39(1H,d,J=2.8 Hz,H-3),3.34(1H,m,H-16α),2.48(1H,s,H-18),1.35(3H,s,CH3-27),1.19(3H,s,CH3-29),1.00(3H,s,CH3-25),0.96(3H,s,CH3-23),0.92(3H,d,J=6.6 Hz,CH3-30),0.88(3H,s,CH3-26),0.78(3H,s,CH3-24);13C-NMR(CD3OD,125 MHz)δ:81.3(C-1),71.8(C-2),80.7(C-3),38.9(C-4),48.9(C-5),19.4(C-6),34.2(C-7),41.8(C-8),48.7(C-9),44.3(C-10),22.4(C-11),130.7(C-12),138.8(C-13),43.1(C-14),29.7(C-15),26.2(C-16),48.5(C-17),54.9(C-18),73.6(C-19),42.5(C-20),27.1(C-21),39.0(C-22),28.3(C-23),22.4(C-24),12.9(C-25),17.7(C-26),24.9(C-27),182.3(C-28),27.3(C-29),16.6(C-30)。
以上数据与文献[10]报道基本一致,故鉴定化合物2为1-β羟基蔷薇酸(1β-hydroxy euscaphic acid)。
化合物3白色粉末(甲醇);EI-MS m/z 489[M+H]+;1H-NMR(CD3OD,400 MHz)δ:5.29(1H,br s,H-12),3.92(1H,br d,J=12.0 Hz,H-3),3.31(1H,overlap,H-2),2.49(1H,s,H-18),1.35(3H,s,CH3-27),1.28(3H,s,CH3-29),1.19(3H,s,CH3-25),0.98(3H,s,CH3-23),0.92(3H,d,J=6.8 Hz,CH3-30),0.86(3H,s,CH3-26),0.78(3H,s,CH3-24);13C-NMR(CD3OD,100 MHz)δ:42.2(C-1),67.2(C-2),80.1(C-3),41.2(C-4),49.2(C-5),24.7(C-6),34.0(C-7),39.3(C-8),48.1(C-9),39.5(C-10),27.3(C-11),129.3(C-12),140.0(C-13),
42.7(C-14),29.5(C-15),26.5(C-16),48.6(C-17),55.0(C-18),73.6(C-19),
43.0(C-20),19.3(C-21),39.0(C-22),29.3(C-23),22.4(C-24),17.5(C-25),16.6(C-26),27.0(C-27),182.5(C-28),24.9(C-29),16.9(C-30)。
以上数据与文献[11]报道基本一致,故鉴定化合物3为蔷薇酸(euscaphic acid)。
化合物4白色粉末(甲醇);EI-MS m/z 489[M+H]+;1H-NMR(CD3OD,
400 MHz)δ:5.28(1H,br s,H-12),3.92(1H,br d,J=11.2 Hz,H-3),3.61(1H,m,H-2),2.48(1H,s,H-18),1.34(3H,s,CH3-27),1.19(3H,s,CH3-29),1.01(3H,s,CH3-25),0.96(3H,s,CH3-23),0.92(3H,d,J=6.8 Hz,CH3-30),0.80(3H,s,CH3-26),0.78(3H,s,CH3-24);13C-NMR(CD3OD,100 MHz)δ:47.9(C-1),69.5(C-2),84.5(C-3),40.5(C-4),56.8(C-5),19.3(C-6),33.9(C-7),40.5(C-8),48.1(C-9),39.0(C-10),24.0(C-11),124.7(C-12),140.1(C-13),42.5(C-14),29.5(C-15),29.4(C-16),46.1(C-17),45.2(C-18),82.4(C-19),34.0(C-20),29.2(C-21),36.0(C-22),28.7(C-23),17.6(C-24),16.9(C-25),17.4(C-26),24.9(C-27),182.4(C-28),28.5(C-29),24.9(C-30)。
以上数据与文献[12]报道基本一致,故鉴定化合物4为arjunic acid。
化合物5白色粉末(甲醇);EI-MS m/z 489 [M+H]+;1H-NMR(DMSO-d6,400 MHz)δ:5.15(1H,br s,H-12),4.38(1H,m,H-2),3.41(1H,overlap,H-3),2.48(1H,s,H-18),1.26(3H,s,CH3-27),1.06(3H,s,CH3-29),0.90(3H,s,CH3-25),0.88(3H,s,CH3-23),0.81(3H,d,J=6.8 Hz,CH3-30),0.68(3H,s,CH3-26),0.66(3H,s,CH3-24);13C-NMR(DMSO-d6,100 MHz)δ:47.2(C-1),67.4(C-2),82.5(C-3),38.9(C-4),55.0(C-5),18.4(C-6),32.8(C-7),40.1(C-8),46.9(C-9),38.7(C-10). 23.4(C-11),127.0(C-12),138.9(C-13),41.3(C-14),28.3(C-15),25.4(C-16),47.1(C-17),53.4(C-18),71.9(C-19),41.6(C-20),26.1(C-21),37.5(C-22),29.0(C-23),16.5(C-24),16.5(C-25),18.4(C-26),24.2(C-27),179.3(C-28),26.7(C-29),17.4(C-30)。
以上波谱数据与文献[13]报道基本一致,因此鉴定化合物5为委陵菜酸(tormentic acid)。
化合物6白色粉末(甲醇);ESI-MS m/z 673 [M+Na]+;1H-NMR(CD3OD,400 MHz)δ:5.30(1H,d,J=8.0 Hz,glcH-1),5.29(1H,br s,H-12),2.50(1H,s,H-18),2.61(1H,m,H-3),1.33(3H,s,CH3-27),1.19(3H,s,CH3-29),0.98(3H,d,CH3-25),0.97(3H,d,CH3-23),0.92(3H,d,J=6.4 Hz,CH3-30),0.86(3H,s,CH3-26),0.73(3H,s,CH3-24);13C-NMR(CD3OD,100 MHz)δ:42.6(C-1),67.2(C-2),80.1(C-3),39.5(C-4),49.3(C-5),22.5(C-6),34.1(C-7),41.5(C-8),48.3(C-9),39.4(C-10),24.8(C-11),129.6(C-12),139.7(C-13),42.8(C-14),29.7(C-15),26.5(C-16),48.5(C-17),55.0(C-18),73.7(C-19),43.0(C-20),27.2(C-21),38.3(C-22),29.2(C-23),16.6(C-24),17.0(C-25),19.3(C-26),24.8(C-27),178.6(C-28),27.1(C-29),17.7(C-30),95.8(C-1′),73.9(C-2′),78.6(C-3′),71.2(C-4′),78.3(C-5′),62.5(C-6′)。
以上数据与文献[14]报道基本一致,故鉴定化合物6为刺梨苷(kaiiichigeside F1)。
化合物7白色粉末(甲醇);ESI-MS m/z 673 [M+Na]+;1H-NMR(CD3OD,400 MHz)δ:5.36(1H,d,J=8.0 Hz,glcH-1),5.32(1H,br s,H-12),2.51(1H,s,H-18),1.31(3H,s,CH3-27),1.28(3H,s,CH3-29),1.19(3H,s,CH3-25),1.06(3H,s,CH3-23),0.93(3H,d,J= 5.2 Hz,CH3-30),0.80(3H,s,CH3-26),0.77(3H,s,CH3-24);13C-NMR (CD3OD,100 MHz)δ:48.2(C-1),69.5(C-2),84.6(C-3),39.2(C-4),56.7(C-5),19.7(C-6),34.0(C-7),41.3(C-8),48.7(C-9),40.5(C-10),
24.8(C-11),129.5(C-12),139.7(C-13),42.9(C-14),29.6(C-15),26.5(C-16),48.6(C-17),54.9(C-18),73.6(C-19),42.9(C-20),27.2(C-21),37.0(C-22),29.3(C-23),17.6(C-24),16.6(C-25),17.4(C-26),25.0(C-27),178.6(C-28),28.6(C-29),25.1(C-30),95.8(C-1′),73.8(C-2′),78.2(C-3′),71.0(C-4′),78.6(C-5′),62.3(C-6′)。
以上波谱数据与文献[15]报道基本一致,因此鉴定化合物7为野蔷薇苷(rosamultin)。
化合物8白色粉末(甲醇);ESI-MS m/z 673 [M+Na]+;1H-NMR(CD3OD,400 MHz)δ:5.37(1H,d,J=8.0 Hz,glcH-1),5.32(1H,s,H-12),1.33(3H,s,CH3-27),1.00(3H,s,CH3-29),0.99(3H,s,CH3-25),0.94(3H,s,CH3-23),0.93(3H,s,CH3-30),0.80(3H,s,CH3-26),0.74(3H,s,CH3-24);13C-NMR(CD3OD,100 MHz)δ:48.0(C-1),65.9(C-2),84.5(C-3),40.9(C-4),56.8(C-5),19.7(C-6),33.8(C-7),40.5(C-8),49.2(C-9),39.4(C-10),24.9(C-11),124.8(C-12),144.4(C-13),42.6(C-14),29.5(C-15),28.4(C-16),47.0(C-17),45.0(C-18),82.4(C-19),36.0(C-20),29.5(C-21),33.7(C-22),29.3(C-23),17.7(C-24),17.0(C-25),17.4(C-26),25.0(C-27),178.6(C-28),28.6(C-29),25.1(C-30),95.8(C-1′),73.8(C-2′),78.3(C-3′),71.0(C-4′),78.7(C-5′),62.3(C-6′)。
以上数据与文献[16]报道基本一致,故鉴定化合物8为arjunetin。
化合物9白色粉末(甲醇);ESI-MS m/z 673.5[M+Na]+;1H-NMR(CD3OD,400 MHz)δ:5.37(1H,d,J=8.0 Hz,glcH-1),5.33(1H,m,H-12),1.29(3H,s,CH3-27),1.01(3H,s,CH3-23),0.97(3H,s,CH3-26),0.94(3H,s,CH3-29),0.93(3H,s,CH3-25),0.86(3H,s,CH3-30),0.73(3H,s,CH3-24);13C-NMR(CD3OD,100 MHz)δ:42.7(C-1),67.1(C-2),80.1(C-3),39.5(C-4),49.4(C-5),19.3(C-6),33.3(C-7),41.0(C-8),48.7(C-9),39.5(C-10),24.9(C-11),124.9(C-12),144.4(C-13),42.3(C-14),29.2(C-15),28.4(C-16),47.1(C-17),45.0(C-18),82.4(C-19),35.9(C-20),29.4(C-21),33.8(C-22),29.5(C-23),22.4(C-24),16.9(C-25),17.8(C-26),25.2(C-27),178.6(C-28),28.6(C-29),25.1(C-30),95.8(C-1′),73.9(C-2′),78.7(C-3′),71.0(C-4′),78.3(C-5′),62.3(C-6′)。
以上波谱数据与文献[17]报道的数据基本一致,故鉴定化合物9为2α,3α,19α-trihydroxy-olean-12-en-28-oic acid 28-O-β-D-glucopyranoside。
化合物10白色粉末。
ESI-MS m/z 689[M+ Na]+;1H-NMR(CD3OD,400 MHz)δ:5.35(1H,d,J=8.0 Hz,glcH-1),5.32(1H,br s,H-12),1.29(3H,s,CH3-23),1.08(3H,s,CH3-27),1.01(3H,s,CH3-26),0.94(3H,s,CH3-29),0.94(3H,s,CH3-25),0.71(3H,s,CH3-30);13C-NMR(CD3OD,100 MHz)δ:42.7(C-1),66.9(C-2),74.6(C-3),45.4(C-4),50.0(C-5),19.5(C-6),34.1(C-7),41.0(C-8),49.0(C-9),39.3(C-10),25.0(C-11),124.8(C-12),144.4(C-13),42.5(C-14),29.4(C-15),28.4(C-16),47.1(C-17),45(C-18),82.4(C-19),35.9(C-20),29.5(C-21),33.3(C-22),23.1(C-23),65.8(C-24),17.3(C-25),17.7(C-26),25.2(C-27),178.6(C-28),28.6(C-29),25.0(C-30),95.8(C-1′),71.0(C-2′),78.3(C-3′),73.9(C-4′),78.7(C-5′),62.3(C-6′)。
以上光谱数据与文献[18]报道的数据基本一致,故鉴定化合物10为2α,3α,19α,24-tetrahydroxyolean-12-en-28-oic-acid
28-O-β-D-glucopyranosyl ester。
化合物11白色粉末,ESI-MS m/z 127[M+H]+。
1H-NMR(CD3OD,400 Hz)δ:6.21(2H,d,J=8.4 Hz,H-4,6),6.38(1H,t,J=8.4 Hz,H-5);以上波谱数据与文献[19]报道的数据基本一致。
故鉴定化合物11为焦性没食子酸(pyrogallic acid)。
化合物12白色粉末(甲醇);ESI-MS m/z 599.5[M+ Na]+;1H-NMR(C5D5N,400 MHz)δ:5.37(1H,br s,H-6),4.59(1H,d,J=10.4 Hz,H-1′);13C-NMR (C5D5N,100 MHz)δ:37.6(C-1),30.3(C-2),78.2(C-3),39.4(C-4),141.0(C-5),122.0(C-6),32.3(C-7),32.1(C-8),50.4(C-9),36.5(C-10),21.4(C-11),39.4(C-12),42.6(C-13),56.9(C-14),24.6(C-15),28.7(C-16),56.3(C-17),12.1(C-18),19.3(C-19),36.5(C-20),19.1(C-21),34.3(C-22),26.4(C-23),46.1(C-24),29.5(C-25),19.5(C-26),20.1(C-27),23.5(C-28),12.3(C-29),102.6(C-30),75.4(C-31),78.6(C-32),71.8(C-33),78.2(C-34),62.9(C-35)。
以上数据与文献[20]报道的数据基本一致,故鉴定化合物12为β-胡萝卜苷(daucosterol)。
化合物13油状物(甲醇),EI-MS m/z 175[M+H]+;1H-NMR(CD3OD,400 Hz)δ:3.70(1H,m,H-2),3.42(1H,dd,J=10.4,6.4 Hz,H-1a),3.50(1H,dd,J=10.4,5.8 Hz,H-1b),0.91(3H,t,CH3-10)。
同时与对照品对照确定为1,2-癸二醇(1,2-decanediol)。
[致谢]核磁数据和质谱分别由贵州省中国科学院天然产物化学重点实验室张建新研究员与王道平副研究员测定。
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