中草药  2014, Vol. 45 Issue (11): 1515-1520
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牛大力的化学成分研究
王呈文1,3, 陈光英1, 宋小平1, 陈文豪1, 舒火明1,2 , 韩长日1 , 纪明慧1    
1. 海南师范大学 热带药用植物化学教育部重点实验室, 海南 海口 571127;
2. 海南经济贸易职业技术学院, 海南 海口 571158;
3. 汕头职业技术学院, 广东 汕头 515078
摘要目的 研究牛大力(美丽崖豆藤Millettia speciosa的干燥根)中的化学成分。方法 采用大孔吸附树脂、硅胶柱色谱、葡聚糖凝胶柱色谱和重结晶等分离方法进行分离纯化,综合运用各种波谱手段和理化性质鉴定各化合物的结构。结果 从牛大力95%乙醇提取物中分离纯化得到16个化合物,分别鉴定为7-羰基-β-谷甾醇(1)、橙黄胡椒酰胺乙酸酯(2)、紫菀酮(3)、顺丁烯二酸(4)、补骨脂素(5)、N-甲基金雀花碱(6)、咖啡酸羽扇豆醇酯(7)、双去氧基姜黄素(8)、香草酸(9)、丁香酸(10)、6-甲氧基二氢血根碱(11)、甘草酸(12)、(E)-3,3’-二甲氧基-4,4’-二羟基-1,2-二苯乙烯(13)、五味子醇乙(14)、7-羟基千金二萜醇(15)、苷松新酮(16)。结论 所有化合物均为首次从该植物中分离得到,其中化合物378111316为首次从该科植物中分离得到,化合物246910为首次从该属植物中分离得到。
关键词美丽崖豆藤     紫菀酮     补骨脂素     咖啡酸羽扇豆醇酯     丁香酸     五味子醇乙     苷松新酮    
Chemical constituents from roots of Millettia speciosa
WANG Cheng-wen1,3, CHEN Guang-ying1, SONG Xiao-ping1, CHEN Wen-hao1, SHU Huo-ming1,2, HAN Chang-ri1, JI Ming-hui1    
1. Key Laboratory of Tropical Medicinal Plant Chemistry, Ministry of Education, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571127, China;
2. Hainan College of Economics and Business, Haikou 571158, China;
3. Shantou Polytechnic, Shantou 515078, China
Abstract: Objective To study the chemical constituents from the roots of Millettia speciosa (Leguminosae). Methods Compounds in the 95% ethanol extract from the air-dried roots of M. speciosa were isolated by chromatography on silica gel column together with recrystallization, and their structures were identified by their physicochemical characteristics and spectral features. Results Sixteen components were isolated from the air-dried roots of M. speciosa and identified as 7-oxo-β-sitosterol (1), aurantiamide acetate (2), shionone (3), maleic acid (4), psoralen (5), N-methylcytisine (6), lupeol caffeate (7), bisdemethoxycurcumin (8), vanillic acid (9), syringic acid (10), 6-methoxydihdyrosanguinarine (11), glycyrrhizic acid (12), (E)-3, 3'-dimethoxy-4, 4'-dihydroxystilbene (13), schisandrol B (14), 7-hydroxylathyrol (15), and nardosinone (16). Conclusion All the compounds are isolated from this plant for the first time, and compounds 3, 7, 8, 11, and 1316 are isolated from the plants of Leguminosae for the first time, compounds 2, 46, 9, 10 are isolated from the plants of Millettia Wight et Arn. for the first time.
Key words: Millettia speciosa Champ.     shionone     psoralen     lupeol caffeate     syringic acid     schisandrol B     nardosinone    

牛大力(俗名)是豆科(Leguminosae)崖豆藤属Millettia Wight et Arn. 植物美丽崖豆藤Millettia speciosa Champ. 的干燥根,在我国已有悠久的临床使用历史,牛大力性味甘、平,具有补虚润肺、强筋活络的功效,临床主要用来治疗肺热咳嗽、风湿性关节炎、腰肌劳损、胃溃疡、慢性肝炎、肺结核等疾病。牛大力为传统药食两用中药材,在我国南方地区被广泛用作煲汤原料,制作药膳、药酒等,补腰肾、强筋骨功效显著。早在20世纪70年代,牛大力作为壮腰健肾丸、强力健身胶囊的原料已用于中成药的生产[1, 2]。现有的药理研究表明,牛大力具有免疫调节、降血糖、抗氧化和清除自由基等功效[2, 3]。目前的研究表明牛大力含有三萜、黄酮、酚类、木脂素等化学成分[4, 5, 6, 7]。本实验对牛大力的化学成分进行深入的研究,从中分离得到16个单体化合物,分别鉴定为7-羰基-β-谷甾醇(7-oxo-β-sitosterol,1)、橙黄胡椒酰胺乙酸酯(aurantiamide acetate,2)、紫菀酮(shionone,3)、顺丁烯二酸(maleic acid,4)、补骨脂素(psoralen,5)、N-甲基金雀花碱(N- methylcytisine,6)、咖啡酸羽扇豆醇酯(lupeol caffeate,7)、双去氧基姜黄素(bisdemethoxy- curcumin,8)、香草酸(vanillic acid,9)、丁香酸(syringic acid,10)、6-甲氧基二氢血根碱(6-methoxy- dihdyrosanguinarine,11)、甘草酸(glycyrrhizic acid,12)、(E)-3,3′-二甲氧基-4,4′-二羟基-1,2-二苯乙烯[(E)-3,3′-dimethoxy-4,4′-dihydroxy-1,2-stilbene,13]、五味子醇乙(schisandrol B,14)、7-羟基千金二萜醇(7-hydroxylathyrol,15)、苷松新酮(nardosinone,16)。所有化合物均为首次从该植物中分离得到,其中化合物378111316为首次从该科植物中分离得到,化合物246910为首次从该属植物中分离得到。

1 仪器与材料

Bruker AV—400型核磁共振仪(瑞士布鲁克公司);SephadexLH—20(美国Pharmacia公司);薄层硅胶GF254,柱色谱硅胶(100~200、200~300目)均青岛海洋化工厂产品;XT5A显微熔点测定仪(北京市科仪电光仪器厂)。

牛大力2011年5月采自海南省五指山市,经海南师范大学生命科学院钟琼芯教授鉴定为豆科崖豆藤属植物美丽崖豆藤Millettia speciosa Champ. 的干燥根,样本(20110511MS)保存在海南省热带药用植物化学教育部重点实验室。

2 提取与分离

取干燥的牛大力25 kg,粉碎得粉末,用95%乙醇浸泡,加热回流提取3次,合并提取液,减压浓缩后得到乙醇提取物。浸膏乙醇提取物用水悬溶,依次用一定体积的石油醚(60~90 ℃)、氯仿、醋酸乙酯反复多次萃取。萃取液减压浓缩,依次得到石油醚部位86.9 g、氯仿部位67.3 g、醋酸乙酯部位65.4 g。石油醚萃取部位采用硅胶柱色谱分离,依次用石油醚-醋酸乙酯(9∶1→0∶1)梯度洗脱,浓缩收集的流分,合并相似流分,最后得到12个组分(S1~S12)。S7经过重结晶得到化合物2(12 mg)。S7再通过正相硅胶柱色谱,石油醚-醋酸乙酯(9∶1→0∶1)梯度洗脱,合并相似流分,得到10个组分(S7-1~S7-10)。S7-5经过反复正相硅胶柱色谱以及制备薄层色谱,得到化合物1(8 mg);S7-6经过反复正相硅胶柱色谱以及制备薄层板,得到化合物3(9 mg)。

氯仿部位采用硅胶柱色谱分离,以石油醚-醋酸乙酯(9∶1→0∶1)梯度洗脱,再用醋酸乙酯-甲醇(19∶1→1∶1)梯度洗脱,浓缩收集的流分,合并相似流分,得到16个组分(L1~L16)。L5、L6、L7采用硅胶柱色谱,分别以石油醚-醋酸乙酯(9∶1→0∶1)梯度洗脱,合并相似流分,最后分别得到8个组分(L5-1~L5-8)、7个组分(L6-1~L6-7)、10个组分(L7-1~L7-10)。L5-3、L6-3采用硅胶柱色谱,分别以石油醚-醋酸乙酯(10∶1→0∶1)梯度洗脱,再经制备薄层色谱纯化得到化合物16(5 mg)、15(6 mg)。L7-4、L7-6经硅胶柱色谱,分别以石油醚-醋酸乙酯(15∶1→0∶1)梯度洗脱,再经制备薄层色谱纯化得到化合物13(6 mg)、14(5 mg)。

醋酸乙酯部位采用硅胶柱色谱及凝胶柱色谱分离。采用硅胶柱色谱,以石油醚-醋酸乙酯(4∶1→0∶1)梯度洗脱,然后再用醋酸乙酯-甲醇(19∶1→1∶1)进行梯度洗脱,浓缩收集的流分,合并相似流分,最后得到9个组分(Y1~Y9),其中Y2(15 g)和Y6(13 mg)的量最多。Y2采用硅胶柱色谱,以石油醚-醋酸乙酯(4∶1→0∶1)梯度洗脱,合并相似流分,最后得到8个组分(Y2-1~Y2-8)。Y2-2、Y2-3、Y2-4、Y2-5分别用Sephadex LH-20分离,合并相似流分,最后分别得到7个组分(Y2-2-1~Y2-2-7)、6个组分(Y2-3-1~Y2-3-6)、7个组分(Y2-4-1~Y2-4-7)、7个组分(Y2-5-1~Y2-5-7)。Y2-2-3、Y2-2-5、Y2-3-4、Y2-3-2、Y2-4-6、Y2-5-3经制备薄层色谱纯化得到化合物5(7 mg)、4(10 mg)、6(7 mg)、7(5 mg)、9(6 mg)和10(5 mg)、8(7 mg)和11(4 mg)。Y6用Sephadex LH-20分离,合并相似流分,最后得到8个组分(Y6-1~Y6-8)。Y6-6经反复Sephadex LH-20以及反相硅胶得到化合物12(6 mg)。

3 结构鉴定

化合物1:白色针状结晶(氯仿),mp 139~140 ℃,ESI-MS m/z: 429 [M+H]+1H-NMR (400 MHz,CDCl3) δ: 5.70 (1H,s,H-6),3.68 (1H,m,H-3),1.20 (3H,s,H-19),0.93 (3H,d,J = 5.8 Hz,H-21),0.85 (3H,d,J = 7.2 Hz,H-27),0.83 (3H,t,J = 10.2 Hz,H-29),0.80 (3H,d,J = 7.2 Hz,H-26),0.68 (3H,s,H-18);13C-NMR (100 MHz,CDCl3) δ: 202.5 (C-7),165.3 (C-5),126.1 (C-6),70.6 (C-3),54.7 (C-17),50.0 (C-9,14),45.8 (C-8),45.4 (C-24),43.1 (C-13),41.8 (C-4),38.7 (C-12),38.3 (C-10),36.4 (C-1),36.1 (C-20),34.0 (C-22),31.2 (C-2),29.1 (C-25),28.6 (C-16),26.4 (C-15),26.1 (C-23),23.1 (C-28),21.2 (C-11),19.9 (C-26),19.1 (C-27),19.0 (C-21),17.4 (C-18),12.0 (C-19,29)。以上数据与文献报道一致[8],故鉴定化合物1为7-羰基-β-谷甾醇。

化合物2:白色粉末(氯仿),mp 193~194 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 445 [M+H]+1H-NMR (400 MHz,CDCl3) δ: 7.06~7.73 (15H,m,H-2′~6′,2″~6″,2′′′~6′′′),6.86 (1H,d,J = 7.6 Hz,H-8),6.09 (1H,d,J = 8.0 Hz,H-5),4.79 (1H,m,H-7),4.34 (1H,m,H-4),3.93 (1H,dd,J = 11.4,4.0 Hz,H-3b),3.82 (1H,dd,J = 11.4,4.0 Hz,H-3a),3.22 (1H,dd,J = 13.8,5.8 Hz,H-10b),3.07 (1H,dd,J = 13.5,5.8 Hz,H-10a),2.77 (1H,dd,J = 13.8,7.0 Hz,H-11b),2.73 (1H,dd,J = 13.8,7.0 Hz,H-11a),2.02 (3H,s,H-1);13C-NMR (100 MHz,CDCl3) δ: 170.8 (C-2),170.3 (C-6),167.1 (C-9),136.7 (C-1″),136.6 (C-1′′′),133.6 (C-1′),131.9 (C-4′),129.4 (C-3″),129.3 (C-5″),129.1 (C-3′′′),129.1 (C-5′′′),128.8 (C-2″),128.7 (C-6″),128.6 (C-4″),128.5 (C-2′),128.49 (C-6′),127.1 (C-2′′′),127.1 (C-6′′′),127.0 (C-3′,5′),126.7 (C-4′′′),64.5 (C-3),55.0 (C-7),49.4 (C-4),38.4 (C-10),37.4 (C-11),20.8 (C-1)。以上数据与文献报道一致[9],故鉴定化合物2为橙黄胡椒酰胺乙酸酯。

化合物3:无色针晶(醋酸乙酯),mp 161~162 ℃,ESI-MS m/z: 427 [M+H]+1H-NMR (400 MHz,CDCl3) δ: 5.10 (1H,m,H-21),2.37 (1H,m,H-2a),2.30 (1H,m,H-2b),2.24 (1H,m,H-4),1.98 (1H,m,H-1a),1.91 (1H,overlapped,H-16b),1.74 (1H,m,H-19b),1.72 (1H,overlapped,H-6b),1.69 (3H,s,H-29),1.65 (1H,m,H-20),1.64 (1H,m,H-1b),1.61 (3H,s,H-30),1.57 (1H,overlapped,H-16a),1.54 (1H,overlapped,H-10),1.51 (1H,m,H-12b),1.47 (1H,overlapped,H-11b),1.43 (1H,overlapped,H-7a),1.40 (1H,m,H-20),1.38 (1H,overlapped,H-11a),1.36 (1H,overlapped,H-8),1.32 (1H,overlapped,H-7b),1.30 (1H,overlapped,H-15),1.28 (1H,m,H-18b),1.24 (1H,overlapped,H-6a),1.14 (3H,s,H-27),1.11 (1H,m,H-19a),1.06 (1H,m,H-18a),0.92 (3H,s,H-25),0.91 (1H,overlapped,H-12a),0.90 (3H,s,H-28),0.88 (3H,s,H-26),0.87 (3H,d,J = 6.6 Hz,H-23),0.71 (3H,s,H-24);13C-NMR (100 MHz,CDCl3) δ: 213.3 (C-3),130.9 (C-22),125.2 (C-21),59.6 (C-10),58.2 (C-4),49.9 (C-8),44.5 (C-18),43.6 (C-19),42.8 (C-5),41.5 (C-2),41.1 (C-6),38.6 (C-14),38.5 (C-9),36.9 (C-13),35.3 (C-11),34.7 (C-16),33.0 (C-28),32.3 (C-12),31.8 (C-17),29.2 (C-15),25.8 (C-29),23.2 (C-20),22.3 (C-1),20.6 (C-27),19.6 (C-25),17.9 (C-7),17.6 (C-30),15.2 (C-26),14.7 (C-24),6.8 (C-23)。以上数据与文献报道一致[10, 11],故鉴定化合物3为紫菀酮。

化合物4:白色粉末(甲醇),mp 134~138 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 117 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 6.62 (2H,s,H-2,3);13C-NMR (100 MHz,DMSO-d6) δ: 166.0 (C-1,4),133.9 (C-2,3)。以上数据与文献报道一致[12],故鉴定化合物4为顺丁烯二酸。

化合物5:白色针状晶体(丙酮),mp 162~163 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 187 [M+H]+1H-NMR (400 MHz,CD3COCD3) δ: 8.08 (1H,d,J = 9.6 Hz,H-4),7.96 (1H,s,H-12),7.96 (1H,s,H-5),7.54 (1H,s,H-8),7.03 (1H,s,H-11),6.37 (1H,d,J = 9.6 Hz,H-3);13C-NMR (100 MHz,CD3COCD3) δ: 160.8 (C-2),157.2 (C-7),153.1 (C-9),148.4 (C-12),145.3 (C-4),125.8 (C-6),121.5 (C-5),116.6 (C-10),115.3 (C-3),107.5 (C-11),100.1 (C-8)。以上数据与文献报道一致[13],故鉴定化合物5为补骨脂素。

化合物6:白色针状结晶(丙酮),mp 134~136 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 205 [M+H]+1H-NMR (400 MHz,CD3COCD3) δ: 7.27 (1H,dd,J = 9.0,6.8 Hz,H-4),6.19 (1H,d,J = 9.0 Hz,H-3),6.01 (1H,d,J = 6.8 Hz,H-5),3.88 (1H,d,J = 15.4 Hz,H-10a),3.75 (1H,m,H-10b),3.00 (1H,m,H-7),2.90 (1H,m,H-11a),2.82 (1H,m,H-13a),2.43 (1H,m,H-9),2.24 (1H,m,H-13b),2.19 (1H,m,H-11b),2.08 (3H,s,N-CH3),1.88 (1H,d,J = 12.8 Hz,H-8a),1.75 (1H,d,J = 12.8 Hz,H-8b);13C-NMR (100 MHz,CD3COCD3) δ: 163.5 (C-2),153.1 (C-6),139.2 (C-4),116.7 (C-3),104.2 (C-5),63.4 (C-13),63.0 (C-11),50.6 (C-10),46.4 (N-CH3),36.2 (C-7),28.9 (C-9),26.0 (C-8)。以上数据与文献报道一致[14],故鉴定化合物6N-甲基金雀花碱。

化合物7:白色粉末(丙酮),TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 589 [M+H]+1H-NMR (400 MHz,CD3COCD3) δ: 7.55 (1H,d,J = 15.8 Hz,H-3′),7.17 (1H,s,H-2″),7.05 (1H,d,J = 8.2 Hz,H-6″),6.88 (1H,d,J = 8.2 Hz,H-5″),6.32 (1H,d,J = 15.8 Hz,H-2′),4.73 (1H,brs,H-29a),4.60 (1H,brs,H-29b),4.56 (1H,m,H-3),2.39 (1H,m,H-19),1.71 (3H,s,H-30),1.05,0.98,0.94,0.92,0.89,0.83 (各3H,s,H-23~28);13C-NMR (100 MHz,CD3COCD3) δ: 167.2 (C-1′),151.7 (C-20),146.4 (C-4″),145.4 (C-3′),144.0 (C-3″),127.7 (C-1″),122.5 (C-6″),116.3 (C-2′),115.2 (C-2″),114.6 (C-5″),110.1 (C-29),81.0 (C-3),56.2 (C-5),51.3 (C-9),50.0 (C-18),48.0 (C-19),43.3 (C-14,17),41.6 (C-8),39.1 (C-22),39.0 (C-13),38.7 (C-1),37.9 (C-4),37.6 (C-10),35.6 (C-16),35.1 (C-7),31.4 (C-21),28.4 (C-11),26.4 (C-23),25.6 (C-12),24.6 (C-2),21.8 (C-15),19.5 (C-30),19.0 (C-6),18.8 (C-28),17.1 (C-24),16.7 (C-25),16.6 (C-26),15.1 (C-27)。以上数据与文献报道一致[15],故鉴定化合物7为咖啡酸羽扇豆醇酯。

化合物8:黄色粉末(丙酮),mp 221~222 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 309 [M+H]+1H-NMR (400 MHz,CD3COCD3) δ: 7.61 (2H,d,J = 15.8 Hz,H-7,7′),7.58 (4H,d,J = 8.0 Hz,H-2,6,2′,6′),6.91 (4H,d,J = 8.0 Hz,H-3,5,3′,5′),6.68 (2H,d,J = 15.8 Hz,H-8,8′),5.99 (1H,s,H-10);13C-NMR (100 MHz,CD3COCD3) δ: 184.6 (C-9,9′),160.5 (C-4,4′),141.1 (C-1,1′),131.0 (C-2,2′,6,6′),127.7 (C-7,7′),122.1 (C-8,8′),116.8 (C-3,3′,5,5′),101.8 (C-10)。以上数据与文献报道一致[16],故鉴定化合物8为双去氧基姜黄素。

化合物9:白色粉末(丙酮),mp 177~179 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 169 [M+H]+1H-NMR (400 MHz,CD3COCD3) δ: 7.59 (1H,d,J = 8.3 Hz,H-6),7.57 (1H,s,H-2),6.91 (1H,d,J = 8.1 Hz,H-5),3.90 (3H,s,3-OCH3);13C-NMR (100 MHz,CD3COCD3) δ: 167.9 (1-COOH),152.1 (C-3),148.1 (C-4),124.9 (C-6),123.1 (C-1),115.5 (C-5),113.5 (C-2),56.3 (3-OCH3)。以上数据与文献报道一致[17],故鉴定化合物9为香草酸。

化合物10:无色针状结晶(丙酮),mp 207~208 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 199 [M+H]+1H-NMR (400 MHz,CD3COCD3) δ: 7.33 (2H,s,H-2),3.89 (6H,s,3,5-OCH3);13C-NMR (100 MHz,CD3COCD3) δ: 167.5 (-COOH),148.4 (C-3,5),141.6 (C-4),121.5 (C-1),108.1 (C-2,6),56.7 (3,5-OCH3)。以上数据与文献报道一致[18],故鉴定化合物10为丁香酸。

化合物11:淡黄色粉末(丙酮),mp 190~192 ℃,ESI-MS m/z: 364 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 7.84 (1H,d,J = 8.6 Hz,H-11),7.66 (1H,s,H-4),7.55 (1H,d,J = 8.6 Hz,H-12),7.51 (1H,d,J = 8.2 Hz,H-10),7.22 (1H,s,H-1),6.99 (1H,d,J = 8.2 Hz,H-9),6.14 (2H,d,J = 8.6 Hz,7-OCH2O-8),6.11 (2H,d,J = 14.6 Hz,2-OCH2O-3),5.50 (1H,d,J = 6.3 Hz,H-6),2.86 (3H,s,O-CH3),2.76 (3H,s,N-CH3);13C-NMR (100 MHz,CD3COCD3) δ: 149.2 (C-2),148.8 (C-8),148.2 (C-3),146.2 (C-7),139.5 (C-4b),132.0 (C-12a),127.8 (C-10a),126.7 (C-4a),124.5 (C-12),123.9 (C-10b),120.9 (C-11),117.0 (C-10),114.7 (C-6a),109.3 (C-9),105.2 (C-1),102.8 (7-OCH2O-8),102.3 (2-OCH2O-3),101.1 (C-4),85.1 (C-6),62.1 (-OCH3),41.0 (N-CH3)。以上数据与文献报道一致[19],故鉴定化合物11为6-甲氧基二氢血根碱。

化合物12:白色粉末(甲醇),mp 170~171 ℃,ESI-MS m/z: 823 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 5.39 (1H,s,H-12),4.48 (1H,d,J = 7.6 Hz,H-1″),4.38 (1H,d,J = 7.6 Hz,H-1′),3.54 (1H,s,H-4′,5′),3.39 (1H,s,H-5″),3.28 (3H,s,H-2′,3′,4″),3.18 (1H,s,H-3″),3.03 (2H,s,H-3,2″),2.33 (1H,s,H-9),1.34 (3H,s,H-27),1.10 (3H,s,H-28),1.03 (6H,s,H-25,26),0.94 (3H,s,H-23),0.75 (3H,s,H-29),0.71 (3H,s,H-24);13C-NMR (100 MHz,DMSO-d6) δ: 199.0 (C-11),177.7 (C-30),170.5 (C-6′),170.1 (C-6″),169.7 (C-13),127.3 (C-12),104.6 (C-1″),103.4 (C-1′),88.1 (C-3),82.6 (C-2′),76.1 (C-5″),75.9 (C-3′),75.6 (C-3″),74.9 (C-5′),74.8 (C-2″),71.5 (C-4″),71.3 (C-4′),61.0 (C-9),54.3 (C-5),48.0 (C-18),44.8 (C-8),43.1 (C-20),42.9 (C-14),40.6 (C-19),39.0 (C-4),38.5 (C-1),37.5 (C-22),36.3 (C-10),32.1 (C-7),31.5 (C-17),30.3 (C-21),28.4 (C-29),27.8 (C-28),27.1 (C-23),26.0 (C-15),25.8 (C-16),25.6 (C-2),22.9 (C-27),18.3 (C-26),16.9 (C-6),16.2 (C-25),15.9 (C-24)。以上数据与文献报道一致[20],故鉴定化合物12为甘草酸。

化合物13:白色粉末(氯仿),mp 216~218 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 273 [M+H]+1H-NMR (400 MHz,CDCl3) δ: 7.02 (2H,s,H-2,2′),7.00 (2H,d,J = 8.0 Hz,H-6,6′),6.90 (2H,d,J = 8.0 Hz,H-5,5′),6.88 (2H,s,H-7,7′),5.64 (2H,brs,2×-OH),3.95 (6H,s,2×-OCH3);13C-NMR (100 MHz,CDCl3) δ: 146.7 (C-3,3′),145.3 (C-4,4′),130.2 (C-1,1′),126.5 (C-7,7′),120.1 (C-6,6′),114.6 (C-5,5′),108.0 (C-2,2′),55.9 (2×-OCH3)。以上数据与文献报道一致[21],故鉴定化合物13为 (E)-3,3′-二甲氧基-4,4′-二羟基-1,2-二苯乙烯。

化合物14:无色透明晶体(丙酮),mp 54~56 ℃,TCL紫外灯254 nm下观察有暗斑,ESI-MS m/z: 401 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 6.73 (1H,s,H-4),6.58 (1H,s,H-11),6.00 (2H,d,J = 5.9 Hz,O-CH2-O),3.98 (1H,s,8-OH),3.81 (3H,s,-OCH3),3.72 (3H,s,-OCH3),3.69 (3H,s,-OCH3),3.35 (3H,s,-OCH3),2.66 (1H,d,J = 13.6 Hz,H-6a),2.36 (1H,d,J = 13.3 Hz,H-9a),2.22 (2H,dd,J = 13.6,13.3 Hz,H-6b,9b),1.66 (1H,m,H-7),1.11 (3H,s,H-17),0.69 (3H,d,J = 6.8 Hz,H-18);13C-NMR (100 MHz,DMSO-d6) δ: 151.1 (C-3),150.7 (C-1),147.1 (C-12),140.7 (C-14),139.3 (C-2),134.3 (C-13),133.9 (C-5),133.0 (C-10),122.6 (C-16),122.1 (C-15),111.6 (C-4),105.7 (C-11),100.7 (O-CH2-O),70.7 (C-8),60.3 (-OCH3),60.0 (-OCH3),58.9 (-OCH3),55.5 (-OCH3),40.8 (C-7),40.6 (C-9),33.4 (C-6),30.4 (C-18),15.5 (C-17)。以上数据与文献报道一致[22],故鉴定化合物14为五味子醇乙。

化合物15:白色晶体(丙酮),ESI-MS m/z: 351 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 7.13 (1H,d,J = 11.4 Hz,H-12),5.04 (1H,s,H-17a),4.83 (1H,s,H-17b),4.79 (1H,s,H-5),4.12 (1H,s,H-3),4.06 (1H,d,J = 3.0 Hz,H-7),2.74 (1H,m,H-1a),2.00 (1H,m,H-4),1.85 (1H,m,H-8a),1.69 (2H,m,H-2,8b),1.63 (3H,s,H-20),1.57 (1H,m,H-1b),1.45 (1H,m,H-11),1.31 (1H,m,H-9),1.16 (3H,s,H-18),1.08 (3H,s,H-19),0.97 (3H,d,J = 5.9 Hz,H-16);13C-NMR (100 MHz,DMSO-d6) δ: 201.4 (C-14),151.9 (C-6),146.4 (C-12),133.3 (C-13),109.9 (C-17),87.1 (C-15),77.1 (C-3),75.2 (C-7),65.4 (C-5),52.8 (C-4),46.5 (C-1),37.1 (C-2),32.0 (C-8),31.3 (C-9),28.5 (C-18),27.5 (C-11),24.1 (C-10),16.0 (C-19),13.9 (C-16),12.7 (C-20)。以上数据与文献报道一致[23],故鉴定化合物15为7-羟基千金二萜醇。

化合物16:白色粉末(丙酮),mp 93~95 ℃,ESI-MS m/z: 251 [M+H]+1H-NMR (400 MHz,DMSO-d6) δ: 6.87 (1H,s,H-1),4.87 (1H,t,J = 8.3 Hz,H-7),3.11 (1H,dd,J = 18.6,7.2 Hz,H-8b),2.96 (1H,d,J = 9.5 Hz,H-6),2.29 (1H,d,J = 18.6 Hz,H-8a),2,24 (2H,m,H-2),1.89 (1H,m,H-4),1.48 (2H,m,H-3),1.29 (3H,s,H-13),1.09 (3H,s,H-12),1.05 (3H,s,H-14),0.96 (3H,d,J = 6.5 Hz,H-15);13C-NMR (100 MHz,DMSO-d6) δ: 195.7 (C-9),139.9 (C-10),136.7 (C-1),84.6 (C-11),77.5 (C-7),58.5 (C-6),39.6 (C-8),37.9 (C-5),32.4 (C-4),25.9 (C-14),25.3 (C-2),25.2 (C-3),23.0 (C-13),21.8 (C-12),15.8 (C-15)。以上数据与文献报道一致[24],故鉴定化合物16为苷松新酮。

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