中草药  2017, Vol. 48 Issue (2): 236-240
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翅果油树叶的化学成分研究
王晓丹1, 郭坤1, 郭敬兰2, 李娟3, 路金才1     
1. 沈阳药科大学中药学院 药用植物教研室, 辽宁 沈阳 110016;
2. 山东省科学院生物研究所, 山东 济南 250000;
3. 琪尔康翅果生物制品有限公司, 山西 临汾 042100
摘要: 目的 对翅果油树 Elaeagnus mollis叶的化学成分进行研究。 方法 利用硅胶柱色谱,Sephadex LH-20柱色谱和制备高效液相色谱等手段进行分离纯化,根据理化性质和波谱数据对化合物进行结构鉴定。 结果 从翅果油树叶70%乙醇提取物中分离得到16个化合物,分别鉴定为山柰酚-3- O-β- D-吡喃葡萄糖苷(1)、山柰酚-3- O-(6"- O-反式对香豆酰基)-β- D-吡喃葡萄糖苷(2)、山柰酚-3- O-(6"- O-顺式对香豆酰基)-β- D-吡喃葡萄糖苷(3)、槲皮素-3- O-α- L-吡喃阿拉伯糖苷(4)、山柰酚-7- O-α- L-吡喃鼠李糖苷(5)、山柰酚-3,7- O-α- L-二吡喃鼠李糖苷(6)、山柰酚-3- O-β- D-吡喃半乳糖-7- O-α- L-吡喃鼠李糖苷(7)、山柰酚-3- O-α- L-呋喃阿拉伯糖-7- O-α- L-吡喃鼠李糖苷(8)、hippophamide(9)、 L-色氨酸(10)、阿江榄仁酸(11)、熊果酸(12)、山柰酚(13)、芦丁(14)、腺苷(15)、β-胡萝卜苷(16)。 结论 化合物3~1015均为首次从胡颓子属植物中分离得到;121112为首次从翅果油植物中分离得到。
关键词: 翅果油树     槲皮素-3- O-α- L-吡喃阿拉伯糖苷     山柰酚-3- O-β- D-吡喃半乳糖-7- O-α- L-吡喃鼠李糖苷     L-色氨酸     腺苷    
Chemical constituents from leaves of Elaeagnus mollis
WANG Xiao-dan1, GUO Kun1, GUO Jing-lan2, LI Juan3, LU Jin-cai1     
1. Department of Traditional Chinese Materia Medica, Shenyang Pharmaceutical University, Shenyang 110016, China;
2. Shandong Academy of Sciences Institute for Biological Studies, Jinan 250000, China;
3. Qwekan Biological Product Co., Ltd., Linfen 042100, China
Abstract: Objective To study the chemical constituents in the leaves of Elaeagnus mollis. Methods Their structures were identified on the basis of silica gel column chromatography and Sephadex LH-20 gel column chromatography, and HPLC methods were used for the separation and purification of chemical constituents. Results Sixteen compounds were isolated from 70% ethanol extracts of the leaves of E. mollis. The structures were identified as kaempferol-3- O-β- D-glucopyranoside(1), kaempferol-3- O-(6"- O- trans- p-coumaroyl)-β- D-glucopyranoside(2), kaempferol-3- O-(6"- O- cis- p-coumaroyl)-β- D-glucopyranoside(3), quercetin-3- O-α- L-arabinopyranoside(4), kaempferol-7- O-α- L-rhamnopyranoside(5), kaempferol-3, 7-di- O-α- L-rhamnopyranoside(6), kaempferol-3- O-β- D-galactopyranosyl-7- O-α- L-rhamnopyranoside(7), kaempferol-3- O-α- Larabinofuranosyl-7- O-α- L-rhamnopyranoside(8), hippophamide(9), L-tryptophan(10), arjunolicacid(11), ursolicacid(12), kaempferol(13), rutin(14), adenosine(15), and β-daucosterol(16). Conclusion Compounds 3-10 and 15 are isolated from the plants of Elaeagnus L. for the first time. Compounds 1, 2, 11, and 12 are isolated from this plant for the first time.
Key words: Elaeagnus mollis Diels.     quercetin-3- O-α- L-arabinopyranoside     kaempferol-3- O-β- D-galactopyranosyl-7- O-α- L-rhamno-pyranoside     L-tryptophan     adenosine    

翅果油树Elaeagnus mollis Diels. 又名泽绿旦、柴禾、车勾子等,为胡颓子科(Elaeagnaceae)胡颓子属Elaeagnus L. 的灌木或落叶小乔木,在我国主要分布于山西和陕西两省[1]。现代药理学研究表明,胡颓子属植物叶子中含有大量黄酮、生物碱、甾体和萜类等活性成分,具有抗菌、抗炎、抗肿瘤等药理作用[2-3]。目前翅果油树的化学成分国内外研究报道较少,为明确翅果油树中化学成分,寻求新的生物活性物质,本实验对其叶的化学成分进行研究,分离并鉴定了16个化合物,分别鉴定为山柰酚- 3-O-β-D-吡喃葡萄糖苷(kaempferol-3-O-β-D- glucopyranoside,1)、山柰酚-3-O-(6″-O-反式对香豆酰基)-β-D-吡喃葡萄糖苷 [kaempferol-3-O-(6″-O- trans-p-coumaroyl)-β-D-glucopyranoside,2]、山柰酚-3-O-(6″-O-顺式对香豆酰基)-β-D-吡喃葡萄糖苷 [kaempferol-3-O-(6″-O-cis-p-coumaroyl)-β-D-gluco- pyranoside,3]、槲皮素-3-O-α-L-吡喃阿拉伯糖苷(quercetin-3-O-α-L-arabinopyranoside,4)、山柰酚- 7-O-α-L-吡喃鼠李糖苷(kaempferol-7-O-α-L- rhamnopyranoside,5)、山柰酚-3,7-O-α-L-二吡喃鼠李糖苷(kaempferol-3,7-di-O-α-L-rhamnopyranoside,6)、山柰酚-3-O-β-D-吡喃半乳糖-7-O-α-L-吡喃鼠李糖苷(kaempferol-3-O-β-D-galactopyranosyl-7-O-α- L-rhamnopyranoside,7)、山柰酚-3-O-α-L-呋喃阿拉伯糖-7-O-α-L-吡喃鼠李糖苷(kaempferol-3-O-α-L- arabinofuranosyl-7-O-α-L-rhamnopyranoside,8)、hippophamide(9)、L-色氨酸(L-tryptophan,10)、阿江榄仁酸(arjunolic acid,11)、熊果酸(ursolic acid,12)、山柰酚(kaempferol,13)、芦丁(rutin,14)、腺苷(adenosine,15)、β-胡萝卜苷(β- daucosterol,16)。

1 仪器与材料

Bruker AV-400、AV-600核磁共振波谱仪(TMS内标,瑞士Bruker公司);Bruker esquire 2000型低分辨质谱仪(瑞士Bruker公司);Yanaco MP-S3显微熔点测定仪(日本岛津公司);Agilent 1260高效液相色谱仪(美国安捷伦公司);Shimadzu SPD-20A制备型高效液相色谱仪(日本岛津公司);SephadexLH-20(美国Pharmacia Biotech公司);薄层色谱和柱色谱用硅胶(青岛海洋化工有限公司);其他试剂(分析纯和色谱纯,市售)。

翅果油树叶子于2014年10月采自山西省临汾市乡宁县,经沈阳药科大学中药学院药用植物教研室路金才教授鉴定为胡颓子科胡颓子属植物翅果油树Elaeagnus mollis Diels. 的叶。

2 提取与分离

干燥的翅果油树叶(16 kg)经粉碎后,用15倍量的70%乙醇回流提取3次,每次1.5 h,滤过提取液,合并滤液,减压回收溶剂,依次用石油醚、二氯甲烷、醋酸乙酯和水饱和正丁醇萃取得到石油醚萃取物280 g、二氯甲烷萃取物185 g、醋酸乙酯萃取物68 g、正丁醇萃取物400 g。正丁醇部位经HPD 400大孔树脂(乙醇-水20∶80、30∶70、40∶60、60∶40、80∶20)梯度洗脱,分成5个流分Fr. 1~5。其中Fr. 5(10 g)经反复硅胶柱色谱分离,二氯甲烷-甲醇(100∶0→0∶100)梯度洗脱,得到化合物9(8 mg)、11(8 mg)、12(20 mg)。Fr. 4(30 g)经反复硅胶柱色谱分离,二氯甲烷-甲醇(20∶1→0∶10)梯度洗脱,Sephadex LH-20柱色谱(甲醇-水)和制备型高效液相色谱(甲醇-水、乙腈-水)分离,得到化合物1(10 mg)、2(50 mg)、3(10 mg)、15(10 mg)、16(40 mg)。Fr. 3(80 g)经反复硅胶柱色谱分离,二氯甲烷-甲醇(8∶1→0∶1)梯度洗脱,Sephadex LH-20柱(甲醇-水)和制备型高效液相色谱(乙腈-水40∶60)分离得到的化合物4(10 mg)、5(40 mg)、6(50 mg)、7(15 mg)、8(800 mg)、10(20 mg)、13(20 mg)、14(15 mg)。

3 结构鉴定

化合物1:淡黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 326~328 ℃,ESI-MS m/z: 449 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 12.62 (1H,s,5-OH),10.85 (1H,s,7-OH),10.17 (1H,s,4′-OH),8.04 (2H,d,J = 8.8 Hz,H-2′,6′),6.88 (2H,d,J = 8.8 Hz,H-3′,5′),6.43 (1H,d,J = 2.1 Hz,H-8),6.23 (1H,d,J = 2.1 Hz,H-6),5.46 (1H,d,J = 7.2 Hz,H-1″);13C-NMR (100 MHz,DMSO-d6) δ: 156.4 (C-2),133.3 (C-3),177.6 (C-4),161.3 (C-5),98.9 (C-6),164.2 (C-7),93.7 (C-8),156.3 (C-9),100.9 (C-10),121.0 (C-1′),133.3 (C-2′,6′),115.2 (C-3′,5′),160.0 (C-4′),100.9 (C-1″),74.3 (C-2″),76.5 (C-3″),69.9 (C-4″),77.6 (C-5″),60.9 (C-6″)。以上数据与文献报道[4]基本一致,故鉴定化合物1为山柰酚-3-O-β-D-吡喃葡萄糖苷。

化合物2:黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 256~259 ℃,ESI-MS m/z: 595 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 12.59 (1H,s,5-OH),8.0 (2H,d,J = 8.8 Hz,H-2′,6′),7.36 (2H,d,J = 8.3 Hz,H-2′′′,6′′′),7.35 (1H,d,J = 15.4 Hz,H-7′′′),6.89 (2H,d,J = 8.6 Hz,H-3′′′,5′′′),6.79 (2H,d,J = 8.6 Hz,H-3′,5′),6.39 (1H,d,J = 2.0 Hz,H-8),6.16 (1H,d,J = 2.0 Hz,H-6),6.13 (1H,d,J = 16.0 Hz,H-8′′′),5.46 (1H,d,J = 7.4 Hz,H-1″),4.28 (1H,d,J = 10.3 Hz,H-6b″),4.04 (1H,dd,J = 11.9,6.3 Hz,H-6a″);13C-NMR (100 MHz,DMSO-d6) δ: 159.2 (C-2),133.5 (C-3),177.9 (C-4),161.6 (C-5),100.0 (C-6),164.7 (C-7),94.8 (C-8),156.8 (C-9),105.6 (C-10),125.7 (C-1′),131.3 (C-2′),115.5 (C-3′),161.4 (C-4′),115.5 (C-5′),131.3 (C-6′),104.3 (C-1″),74.6 (C-2″),74.7 (C-3″),70.4 (C-4″),76.7 (C-5″),63.4 (C-6″),125.3 (C-1′′′),130.6 (C-2′′′),116.2 (C-3′′′),160.3 (C- 4′′′),116.2 (C-5′′′),130.6 (C-6′′′),145.0 (C-7′′′),114.1 (C-8′′′),166.6 (C-9′′′)。以上数据与文献报道[5]基本一致,故鉴定化合物2为山柰酚-3-O-(6″-O-反式对香豆酰基)-β-D-吡喃葡萄糖苷。

化合物3:黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 225~229 ℃,ESI-MS m/z: 595 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 12.57 (1H,s,5-OH),7.97 (2H,d,J = 8.6 Hz,H-2′,6′),7.56 (2H,d,J = 8.3 Hz,H-2′′′,6′′′),6.86 (2H,d,J = 8.5 Hz,H-3′,5′),6.72 (2H,d,J = 8.6 Hz,H-3′′′,5′′′),6.38 (1H,d,J = 1.1 Hz,H-8),6.22 (1H,d,J = 1.1 Hz,H-6),5.48 (1H,d,J = 12.8 Hz,H-7′′′),5.43 (1H,d,J = 7.2 Hz,H-1″),4.18 (1H,d,J = 10.8 Hz,H-6b″),4.16 (1H,d,J = 12.8 Hz,H-8′′′),4.10 (1H,dd,J = 11.7,6.0 Hz,H-6a″);13C-NMR (100 MHz,DMSO-d6) δ: 159.2 (C-2),133.5 (C-3),177.9 (C-4),161.6 (C-5),100.0 (C-6),164.7 (C-7),94.8 (C-8),156.8 (C-9),105.6 (C-10),125.7 (C-1′),131.3 (C-2′),115.5 (C-3′),161.4 (C-4′),115.5 (C-5′),131.3 (C-6′),104.3 (Glc-C-1″),74.6 (C-2″),74.7 (C-3″),70.4 (C-4″),76.7 (C-5″),63.4 (C-6″),125.3 (C-1′′′),130.6 (C-2′′′),116.2 (C-3′′′),160.3 (C-4 ′′′),116.2 (C-5′′′),130.6 (C-6′′′),145.0 (C-7′′′),114.1 (C-8′′′),166.6 (C-9′′′)。以上数据与文献报道[5]基本一致,故鉴定化合物3为山柰酚-3-O-(6″-O-顺式对香豆酰基)-β-D-吡喃葡萄糖苷。

化合物4:黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 186~188 ℃,ESI-MS m/z: 435 [M+H]+1H-NMR (400 MHz,MeOD) δ: 7.66 (1H,dd,J = 2.2,8.5 Hz,H-6′),7.51 (1H,d,J = 2.2 Hz,H-2′),6.84 (1H,d,J = 8.5 Hz,H-5′),6.40 (1H,d,J = 1.9 Hz,H-8),6.19 (1H,d,J = 1.9 Hz,H-6),5.28 (1H,d,J = 5.2 Hz,H-1″);13C-NMR (100 MHz,MeOD) δ: 156.4 (C-2),134.2 (C-3),177.8 (C-4),156.8 (C-5),99.2 (C-6),161.6 (C-7),94.0 (C-8),156.8 (C-9),104.2 (C-10),101.9 (C-1′),156.6 (C-2′),145.5 (C-3′),149.1 (C-4′),115.8 (C-5′),122.5 (C-6′),101.9 (C-1″),66.6 (C-2″),71.2 (C-3″),72.1 (C-4″),64.7 (C-5″)。以上数据与文献报道[6]基本一致,故鉴定化合物4为槲皮素-3-O-α-L-吡喃阿拉伯糖苷。

化合物5:黄色针状结晶(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 236~238 ℃,ESI-MS m/z: 433 [M+H]+1H-NMR (400 MHz,MeOD) δ: 8.10 (2H,d,J = 8.0 Hz,H-2′,6′),6.90 (2H,d,J = 8.3 Hz,H-3′,5′),6.73 (1H,s,H-8),6.41 (1H,s,H-6),5.57 (1H,s,H-1′),4.03 (1H,brs,H-5″),3.85 (1H,dd,J = 9.2,2.6 Hz,H-3″),3.62 (1H,m,H-2″),3.49 (1H,t,J = 9.4 Hz,H-4″),1.27 (3H,d,J = 6.0 Hz,H-6″);13C-NMR (100 MHz,MeOD) δ: 147.4 (C-2),136.0 (C-3),176.1 (C-4),160.9 (C-5),98.6 (C-6),161.2 (C-7),94.0 (C-8),155.3 (C-9),104.8 (C-10),122.1 (C-1′),129.5 (C-2′,6′),115.0 (C-3′,5′),159.5 (C-4′),98.4 (C-1″),70.3 (C-2″),70.7 (C-3″),72.2 (C-4″),69.8 (C-5″),16.7 (C-6″)。以上数据与文献报道[7]基本一致,故鉴定化合物5为山柰酚-7-O-α-L-吡喃鼠李糖苷。

化合物6:淡黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 204~207 ℃,ESI-MS m/z: 601 [M+Na]+1H-NMR (400 MHz,DMSO-d6) δ: 7.80 (2H,d,J = 8.7 Hz,H-2′,6′),6.93 (2H,d,J = 8.7 Hz,H-3′,5′),6.79 (1H,d,J = 1.9 Hz,H-6),6.46 (1H,d,J = 2.0 Hz,H-8),5.56 (1H,brs,H-1),5.31 (1H,brs,H-1″),1.14 (3H,d,J = 6.0 Hz,CH3″),0.81 (3H,d,J = 5.6 Hz,CH3′′′);13C-NMR (400 MHz,DMSO-d6) δ: 156.6 (C-2),135.1 (C-3),178.4 (C-4),161.4 (C-5),99.9 (C-6),162.2 (C-7),95.1 (C-8),158.3 (C-9),106.3 (C-10),120.8 (C-1′),131.2 (C-2′,6′),116.0 (C-3′,5′),160.6 (C-4′),102.4 (C-1″),70.6 (C-2″),71.6 (C-3″),72.1 (C-4″),70.8 (C-5″),18.4 (C-6″),102.4 (C-1′′′),70.8 (C-2′′′),71.2 (C-3′′′),72.1 (C-4′′′),70.3 (C-5′′′),18.0 (C-6′′′)。以上数据与文献报道[8]基本一致,故鉴定化合物6为山柰酚-3,7-O-α-L-二吡喃鼠李糖苷。

化合物7:黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 236~239 ℃,ESI-MS m/z: 595 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 12.6 (1H,s,5-OH),8.1 (2H,d,J = 7.7 Hz,H-2′,6′),6.9 (2H,d,J = 8.2 Hz,H-3′,5′),6.8 (1H,s,H-8),6.4 (1H,s,H-6),5.4 (1H,d,J = 7.5 Hz,H-1″),1.1 (1H,d,J = 5.3 Hz,H-6′′′);13C-NMR (100 MHz,DMSO-d6) δ: 160.7 (C-2),134.0 (C-3),178.2 (C-4),161.4 (C-5),98.9 (C-6),162.1 (C-7),195.0 (C-8),56.4 (C-9),106.1 (C-10),121.1 (C-1′),131.5 (C-2′,6′),115.6 (C-3′,5′),161.3 (C-4′),102.0 (C-1″),71.7 (C-2″),73.6 (C-3″),68.4 (C-4″),76.3 (C-5″),60.7 (C-6″),99.9 (C-1′′′),70.5 (C-2′′′),70.7 (C-3′′′),72.1 (C-4′′′),70.3 (C-5′′′),18.4 (C-6′′′)。以上数据与文献报道[9]基本一致,故鉴定化合物7为山柰酚-3-O-β-D-吡喃半乳糖-7-O-α-L-吡喃鼠李糖苷。

化合物8:淡黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 249~252 ℃,ESI-MS m/z: 565 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 8.13 (2H,d,J = 8.8 Hz,H-2′,6′),6.91 (2H,d,J = 8.9 Hz,H-3′,5′),6.84 (1H,d,J = 2.0 Hz,H-8),6.46 (1H,d,J = 2.0 Hz,H-6),5.57 (1H,s,H-6′′′),5.36 (1H,d,J = 5.1 Hz,H-1″),1.13 (3H,d,J = 6.1 Hz,-CH3′′′);13C-NMR (100 MHz,DMSO-d6) δ: 156.4 (C-2),134.3 (C-3),178.2 (C-4),161.3 (C-5),98.8 (C-6),162.1 (C-7),95.1 (C-8),159.2 (C-9),101.7 (C-10),121.0 (C-1′),131.6 (C-2′,6′),115.8 (C-3′,5′),160.7 (C-4′),106.1 (C-1″),82.4 (C-2″),72.1 (C-3″),86.3 (C-4″),64.7 (C-5″),99.9 (C-1′′′),70.1 (C-2′′′),71.2 (C-3′′′),72.0 (C-4′′′),70.3 (C-5′′′),18.4 (C-6′′′)。以上数据与文献报道[10]基本一致, 故鉴定化合物8为山柰酚-3-O-α-L-呋喃阿拉伯糖-7-O-α-L-吡喃鼠李糖苷。

化合物9:白色结晶(甲醇),改良碘化铋钾反应呈阳性。mp 263~266 ℃,ESI-MS m/z: 265 [M+Na]+1H-NMR (600 MHz,MeOD) δ: 8.62 (1H,s,NH-1),7.11 (1H,d,J = 8.6 Hz,H-12),6.70 (1H,d,J = 2.2 Hz,H-9),6.57 (1H,dd,J = 8.6,2.3 Hz,H-11),4.86 (1H,t,J = 7.4 Hz),4.25 (1H,dd,J = 12.9,5.3 Hz,H-5a),2.96 (1H,td,J = 12.1,5.1 Hz,H-5b),2.55~2.67 (2H,m,H-6),2.50~2.55 (1H,m,H-15b),2.43~2.50 (1H,m,H-14b),2.24~2.31 (1H,m,H-15a),1.75~1.82 (1H,m,H-14a);13C-NMR (150 MHz,MeOD) δ: 144.6 (C-2),63.3 (C-3),46.4 (C-5),30.3 (C-6),114.7 (C-7),136.7 (C-8),111.6 (C-9),160.0 (C-10),120.5 (C-11),121.0 (C-12),140.0 (C-13),34.9 (C-14),40.6 (C-15),181.9 (C-16)。以上数据与文献报道[11]基本一致,故鉴定化合物9为hippophamide。

化合物10:淡黄色粉末(甲醇),与茚三酮显色呈蓝色。mp 280~282 ℃,ESI-MS m/z: 203 [M-H]1H-NMR (400 MHz,DMSO-d6) δ: 10.98 (1H,s,NH),7.57 (1H,d,J = 7.8 Hz,H-4),7.36 (1H,d,J = 8.0 Hz,H-7),7.22 (1H,s,H-2),7.07 (1H,t,J = 7.4 Hz,H-6),6.98 (1H,t,J = 7.4 Hz,H-5),3.50 (1H,dd,J = 8.9,4.1 Hz,H-9),3.32 (2H,dd,J = 15.1,3.8 Hz,H-9,8a),2.98 (1H,dd,J = 14.8,9.0 Hz,H-8b);13C-NMR (100 MHz,DMSO-d6) δ: 124.5 (C-2),110.0 (C-3),118.8 (C-4),118.7 (C-5),121.4 (C-6),111.8 (C-7),27.6 (C-8),55.3 (C-9),170.6 (C-10),127.7 (C-3a),136.8 (C-7a)。以上数据与文献报道[12]基本一致,故鉴定化合物10L-色氨酸。

化合物11:白色粉末状晶体(甲醇),Liebermann-Burchard反应为阳性。mp 310~312 ℃,ESI-MS m/z: 489 [M+H]+1H-NMR (400 MHz,MeOD) δ: 1.18 (3H,s,H-27),1.03 (3H,s,H-30),0.95 (3H,s,H-29),0.91 (3H,s,H-25),0.82 (3H,s,H-26),0.69 (3H,s,H-24);13C-NMR (100 MHz,MeOD) δ: 47.6 (C-1),69.7 (C-2),78.2 (C-3),43.0 (C-4),47.9 (C-5),19.1 (C-6),33.3 (C-7),40.6 (C-8),48.2 (C-9),39.0 (C-10),24.0 (C-11),123.4 (C-12),145.4 (C-13),44.1 (C-14),28.8 (C-15),24.6 (C-16),40.6 (C-17),42.7 (C-18),47.2 (C-19),31.6 (C-20),34.9 (C-21),33.8 (C-22),66.3 (C-23),13.9 (C-24),17.5 (C-25),17.8 (C-26),26.5 (C-27),185.3 (C-28),33.6 (C-29),24.0 (C-30)。以上数据与文献报道[13]基本一致,故鉴定化合物11为阿江榄仁酸。

化合物12:白色粉末(甲醇),10%硫酸乙醇溶液显紫色。mp 280~283 ℃,ESI-MS m/z: 457 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 5.11 (1H,brs,H-12),3.42 (1H,dd,J = 14.0,7.0 Hz,H-3),2.09 (1H,d,J = 11.2 Hz,H-18),1.02 (3H,s,H-26),0.90 (3H,s,H-27),0.89 (3H,s,H-29),0.85 (3H,s,H-30),0.79 (3H,s,H-24),0.75 (3H,s,H-23),0.66 (3H,s,H-25);13C-NMR (100 MHz,DMSO-d6) δ: 38.7 (C-1),27.5 (C-2),77.3 (C-3),38.9 (C-4),55.3 (C-5),18.5 (C-6),33.2 (C-7),40.6 (C-8),47.5 (C-9),36.8 (C-10),23.3 (C-11),125.1 (C-12),138.7 (C-13),42.1 (C-14),28.0 (C-15),24.3 (C-16),47.3 (C-17),52.9 (C-18),39.0 (C-19),38.9 (C-20),30.7 (C-21),37.0 (C-22),28.7 (C-23),15.1 (C-24),16.5 (C-25),17.5 (C-26),23.7 (C-27),178.7 (C-28),17.4 (C-29),21.5 (C-30)。以上数据与文献报道[14]基本一致,故鉴定化合物12为熊果酸。

化合物13:黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性。mp 276~278 ℃,ESI-MS m/z: 287 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 12.49 (1H,s,5-OH),10.12 (1H,s,4′-OH),9.42 (1H,s,3-OH),8.05 (1H,d,J = 8.9 Hz,H-2′,6′),6.93 (1H,d,J = 8.9 Hz,H-3′,5′),6.44 (1H,d,J = 2.0 Hz,H-8),6.20 (1H,d,J = 2.0 Hz,H-6)。以上波谱数据与文献报道[15]基本一致,3种不同极性展开条件下,薄层色谱Rf值均与山柰酚对照品一致,故鉴定化合物13为山柰酚。

化合物14:黄色粉末(甲醇),HCl-Mg反应呈阳性,FeCl3反应呈阳性,Molish反应呈阳性。mp 194~196 ℃,ESI-MS m/z: 611 [M+H]+1H-NMR (400 MHz,DMSO-d6),δ: 12.61 (1H,s,5-OH),7.55 (2H,d,H-2′,6′),6.85 (1H,d,J = 8.5 Hz,H-5′),6.39 (1H,d,J = 2.0 Hz,H-8),6.20 (1H,d,J = 2.0 Hz,H-6),5.35 (1H,d,J = 7.3 Hz,H-1″),1.0 (3H,d,-CH3)。以上波谱数据与文献报道[16]基本一致,3种不同极性展开条件下,薄层色谱Rf值均与芦丁对照品一致,故鉴定化合物14为芦丁。

化合物15:白色结晶(甲醇),改良碘化铋钾反应呈阳性。mp 233~234 ℃,ESI-MS m/z: 268 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 8.35 (1H,s,H-8),8.14 (1H,s,H-2),7.33 (2H,s,NH2-6),δ: 5.88 (1H,d,J = 6.2 Hz,H-1′),δ 4.61 (1H,dd,J = 11.4,6.0 Hz,H-3′),4.15 (1H,dd,J = 7.7,4.5 Hz,H-2′),3.97 (1H,d,J = 3.2 Hz,H-4′),3.68 (1H,t,d,J = 11.9,3.8 Hz,H-5′a),3.56 (1H,m,H-5′b);13C-NMR (100 MHz,DMSO-d6) δ: 152.6 (C-2),150.6 (C-4),121.0 (C-5),156.3 (C-6),141.5 (C-8),88.9 (C-1′),74.4 (C-2′),72.5 (C-3′),87.6 (C-4′),62.8 (C-5′)。以上数据与文献报道[17]基本一致,故鉴定化合物15为腺苷。

化合物16:白色针晶(甲醇),10%硫酸-甲醇显紫色。mp 283~284 ℃,ESI-MS m/z: 577 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 5.36 (1H,m,H-6),4.86 (1H,d,J = 8.1 Hz,H-1′),3.73 (1H,m,H-3α),1.12 (3H,s,H-19),0.68~0.92 (12H,m,H-21,26,27,29),0.63 (3H,s,H-18)。以上波谱数据与文献报道[18]基本一致,3种不同极性展开条件下,薄层色谱Rf值均与β-胡萝卜苷对照品一致,故鉴定化合物16为β-胡萝卜苷。

参考文献
[1] 国家环保局, 中国科学院植物所. 中国珍稀濒危重点保护植物名录[M]. 北京: 科学出版社, 1987.
[2] 陆俊, 王珺, 成策, 等. 胡颓子属植物化学成分与药理活性研究进展[J]. 中药材, 2015, 38(4):855–861.
[3] 赵鑫. 胡颓子(胡颓子科), 短肋羽藓(藓纲:羽藓科)和假柴龙树(茶茱萸科)的化学成分和生物活性[D]. 上海:华东师范大学, 2006.
[4] 冯宁, 卢成淑, 南国, 等. 栀子花的化学成分研究[J]. 中草药, 2016, 47(2):200–203.
[5] 张祎, 晁利平, 陈秋, 等. 维药蜀葵花黄酮类成分的分离与结构鉴定[J]. 天津中医药大学学报, 2016, 35(1):36–39.
[6] 张焕莉, 范青飞, 李宁新, 等. 麻欠树皮的化学成分研究[J]. 天然产物研究与开发, 2016, 28(3):366–370.
[7] 王景华, 王亚琳, 楼凤昌. 槐树种子的化学成分研究[J]. 中国药科大学学报, 2001, 32(6):471–473.
[8] 尚小雅, 李帅, 王素娟, 等. 红绒毛羊蹄甲中的黄酮类成分[J]. 中草药, 2009, 40(2):196–199.
[9] 鄢长余, 初正云, 王天敏, 等. 刺槐花的化学成分研究[J]. 中草药, 2010, 41(5):707–709.
[10] Yusifova D Y, Movsumov I S, Garaev E A, et al. Biologically active compounds from Lepidium campestre and pulp from lemon-juice production[J]. Chem Nat Compd, 2015, 51(5): 964–965. DOI:10.1007/s10600-015-1463-9
[11] Yang J O, Zhou W N, Li G, et al. Three new alkaloids from Hippophae rhamnoides Linn. subsp. sinensis Rousi[[J]. Helv Chim Acta, 2015, 98(9): 1287–1290. DOI:10.1002/hlca.v98.9
[12] 徐方方, 范春林, 王磊, 等. 枳椇子的化学成分[J]. 暨南大学学报:自然科学与医学版, 2011, 32(3):304–306.
[13] 孙娟, 金英今, 徐博, 等. 尾叶香茶菜的化学成分及其活性的研究[J]. 延边大学学报:自然科学版, 2014, 40(2):186–188.
[14] 刘艳萍, 黄立刚, 李科凯, 等. 玫瑰树中非生物碱类化学成分研究[J]. 中草药, 2015, 46(6):798–802.
[15] 周彪, 万传星. 甘草地上部分化学成分研究[J]. 中草药, 2016, 47(1):21–25.
[16] Wenkert E, Gottlieb H E. Carbo-13 nuclear magnetic resonance spectroscopy of flavonoid and isoflavonoid compounds[J]. Phytochemistry, 1977, 16(11): 1811–1816. DOI:10.1016/0031-9422(71)85095-1
[17] 黄占波, 宋冬梅, 陈发奎. 天麻化学成分的研究(I)[J]. 中国药物化学杂志, 2005, 15(4):227–228.
[18] Chaturvedula V S P, Prakash I. Isolation of stigmasterol and β-sitosterol from the dichloromethane extract of Rubussua vissimus[J]. Int Cur Pharma J, 2012, 1(9): 239–240.