2016, Vol. 47
波罗蜜根酚性化学成分研究
引用本文 | doi: 10.7501/j.issn.0253-2670.2016.22.005 |
翟晓晓, 钟国跃, 姚鹏程, 林沁华, 元文君, 任刚 . 波罗蜜根酚性化学成分研究[J]. 中草药, 2016, 47(22): 3959-3964.
ZHAI Xiao-xiao, ZHONG Guo-yue, YAO Peng-cheng, LIN Qin-hua, YUAN Wen-Jun, REN Gang . Phenolic constituents from roots of Artocarpus heterophyllus[J]. Chinese Traditional and Herbal Drugs, 2016, 47(22): 3959-3964 .
波罗蜜根酚性化学成分研究
江西中医药大学 中药资源与民族药研究中心, 江西 南昌 330004
摘要:
目的
研究桑科植物波罗蜜Artocarpus heterophyllus根酚性化学成分。
方法
运用ODS、MCI CHP-20P、Sephadex LH-20等柱色谱和高效液相色谱技术从波罗蜜根中分离化合物，并根据理化性质和NMR、MS波谱数据鉴定化合物结构。
结果
从波罗蜜根95%乙醇提取物中分离得到17个酚性化合物，分别鉴定为1-O-阿魏酰甘油（1）、hypargystilbene A（2）、氧化白藜芦醇（3）、2'，3，4'，5，5'-五羟基-顺式-均二苯代乙烯（4）、白藜芦醇（5）、2，4-二羟基苯甲酸乙酯（6）、原儿茶酸乙酯（7）、伞形花内酯（8）、8-（3，3-二甲基烯丙基）-6，7-二羟基香豆素（9）、桑查耳酮A（10）、桂木二氢黄素（11）、styracifolin C（12）、柘树黄酮C（13）、异叶波罗蜜素（14）、环异叶波罗蜜素（15）、artonin A（16）和artonin B（17）。
结论
化合物9为首次从天然产物中分离得到，化合物1、4和6为首次从桑科植物中分离得到，化合物8为首次从波罗蜜属植物中分离得到，化合物3、5、10、11、14和15为首次从波罗蜜中分离得到。
关键词:
波罗蜜根
1-O-阿魏酰甘油
2',3,4',5,5'-五羟基-顺式-均二苯代乙烯
2,4-二羟基苯甲酸乙酯
伞形花内酯
Phenolic constituents from roots of Artocarpus heterophyllus
Research Center of Natural Resources of Chinese Medicinal Materials and Ethnic Medicine, Jiangxi University of Traditional Chinese Medicine, Nanchang 330004, China
Abstract:
Objective
To investigate the phenolic constituents from the roots of Artocarpus heterophyllus.
Methods
Compounds were isolated from the roots of the plant by column chromatography over ODS, MCI GEL CHP-20P, Sephadex LH-20 and by preparative HPLC. Their structures were identified by the analysis of their physicochemical properties and the spectral data of NMR and MS.
Results
Seventeen phenolic compounds were isolated from the roots of the plant, namely 1-O-feruloylglycerol (1), hypargystilbene A (2), oxyresveratrol (3), 2',3,4',5,5'-pentahydroxy-cis-stilbene (4), resveratrol (5), ethyl 2,4-dihydroxybenzoate (6), ethyl 3,4-dihydroxybenzoate (7), umbelliferone (8), 8-(3,3-dimethylallyl)-6,7-dihydroxycoumarin (9), morachalcone A (10), artocarpanone (11), styracifolin C (12), cudraflavone C (13), heterophyllin (14), cycloheterophyllin (15), artonin A (16), and artonin B (17).
Conclusion
It is the first report of the occurrence of compound 9 as a natural product. Compounds 1, 4, and 6 are isolated from the plants of Moraceae family for the first time. Compound 8 is first obtained from the plants of Artocarpus J. R. et G. Forst., while compounds 3, 5, 10, 11, 14, and 15 are first found in A. heterophyllus.
Key words:
roots of Artocarpus heterophyllus
1-O-feruloylglycerol
2',3,4',5,5'-pentahydroxy-cis-stilbene
ethyl 2,4-dihydroxybenzoate
umbelliferone
波罗蜜Artocarpus heterophyllus Lam. 为桑科（Moraceae）波罗蜜属Artocarpus J. R. et G. Forst. 的一种乔木，又称“木波罗”“树波罗”“蜜冬瓜”“牛肚子果”，是世界著名的热带果树，素有“热带珍果”之称。波罗蜜原产于印度，目前印度尼西亚、斯里兰卡、泰国、缅甸、菲律宾、孟加拉、澳大利亚等热带国家均有栽培。波罗蜜的不同部位有不同的药用作用[1-2]，其中，根具有治疗腹泻和发烧的作用；种子具有滋补和镇静的作用；木质部具有缓解抽搐的作用；叶子具有抗梅毒和驱虫的作用；叶灰具有缓解溃疡的作用。已有研究表明，波罗蜜根皮、茎皮及心材中富含酚性成分，具有抗疟疾、抗氧化及广谱抗菌活性[3-7]。本课题组在前期研究中发现，波罗蜜根95%乙醇提取物的氯仿萃取部位对人源组织蛋白酶K具有较强的抑制作用，为了寻找其中的活性物质，本实验对该部位进行了化学成分研究，从中分离了17个化合物，分别鉴定为1-O-阿魏酰甘油（1-O-feruloylglycerol，1）、hypargystilbene A（2）、氧化白藜芦醇（oxyresveratrol，3）、2′,3,4′,5,5′-五羟基-顺式-均二苯代乙烯（2′,3,4′,5,5′- pentahydroxy-cis-stilbene，4)、白藜芦醇（resveratrol，5）、2,4-二羟基苯甲酸乙酯（ethyl 2,4- dihydroxybenzoate，6）、原儿茶酸乙酯（ethyl 3,4-dihydroxybenzoate，7）、伞形花内酯（umbelliferone，8）、8-(3,3-二甲基烯丙基)-6,7-二羟基香豆素[8-(3,3-dimethylallyl)-6,7-dihydroxycoumarin，9]、桑查耳酮A（morachalcone A，10）、桂木二氢黄素（artocarpanone，11）、styracifolin C（12）、柘树黄酮C（cudraflavone C，13）、异叶波罗蜜素（heterop hyllin，14）、环异叶波罗蜜素（cycloheterophyllin，15）、artonin A（16）和artonin B（17）。其中，化合物9为首次从天然产物中分离得到，化合物1、4和6为首次从桑科植物中分离得到，化合物8为首次从波罗蜜属植物中分离得到，化合物3、5、10、11、14和15为首次从波罗蜜中分离得到。
1 仪器与材料Bruker AX-600型核磁共振波谱仪（瑞士布鲁克公司）；Finnigan TSQ 700型质谱仪（美国Finnigan）；Sephadex LH-20（瑞士Pharmacia公司）；Agilent 1260分析型高效液相色谱仪（美国安捷伦科技有限公司）；LC-3000高效液相色谱仪（北京创新通恒科技有限公司）；YMC-pack ODS半制备柱（250 mm×10 mm，5 μm）；MCI CHP-20P树脂、HP-20大孔树脂（日本三菱化学公司）；薄层色谱硅胶板（烟台江友硅胶开发有限公司）；色谱纯甲醇、乙腈（美国天地有限公司）；其他所用试剂均为分析纯（西陇化工股份有限公司）。
波罗蜜根于2013年3月采自广西壮族自治区南宁市，由江西中医药大学中药资源与民族药研究中心慕泽泾讲师鉴定为桑科波罗蜜属波罗蜜Artocarpus heterophyllus Lam. 的根，凭证标本（TCM01-01-2013）保存于江西中医药大学中药资源与民族药研究中心标本室。
2 提取与分离取干燥波罗蜜根17.0 kg，粉碎，过筛，室温下用95%乙醇浸提3次，每次140 L，得浸泡液，滤过合并，滤液减压浓缩得总浸膏1.5 kg。将总浸膏加适量水混悬，依次用石油醚、氯仿、醋酸乙酯、正丁醇萃取，得到石油醚部位213.3 g，氯仿部位574.0 g、醋酸乙酯部位382.0 g、正丁醇部位152.4 g。氯仿部位经大孔树脂柱色谱，用乙醇-水（0∶100→100∶0）梯度洗脱得组分Fr. 1～11。Fr. 4经MCI CHP-20P树脂柱色谱，用乙醇-水（10∶100→100∶0）梯度洗脱，并结合Sephadex LH-20柱色谱（60%甲醇）和半制备高效液相色谱（20%甲醇）得到化合物1（10.0 mg）、3（17.0 mg）。Fr. 5经ODS反相硅胶柱色谱，用乙醇-水（30∶100→100∶0）梯度洗脱，并结合Sephadex LH-20柱色谱（甲醇）和半制备高效液相色谱（40%乙腈）得到化合物4（92.6 mg）、8（2.2 mg）、5（8.9 mg）、7（2.4 mg）、2（5.4 mg）、12（8.0 mg）。Fr. 6经Sephadex LH-20柱色谱（甲醇）洗脱并结合薄层制备色谱得到化合物6（4.0 mg）、9（4.0 mg）。Fr. 7经ODS反相硅胶柱色谱，用乙醇-水（40∶100→100∶0）梯度洗脱，并结合Sephadex LH-20柱色谱（甲醇）和半制备高效液相色谱（60%乙腈）得到化合物10（4.0 mg）、13（10.0 mg）、11（60.0 mg）、14（2.2 mg）、15（12.0 mg）、16（17.0 mg）、17（34.0 mg）。
3 结构鉴定化合物1：浅黄色粉末，ESI-MS m/z: 269.1 [M＋H]+，分子式C13H16O6。1H-NMR (600 MHz,CD3OD) δ: 7.64 (1H,d,J = 15.9 Hz,H-7),7.18 (1H,d,J = 1.9 Hz,H-2),7.07 (1H,dd,J = 8.2,1.9 Hz,H-6),6.80 (1H,d,J = 8.2 Hz,H-5),6.38 (1H,d,J = 15.9 Hz,H-8),4.26 (1H,dd,J = 11.4,4.0 Hz,H-1′α),4.21 (1H,dd,J = 11.4,6.0 Hz,H-1′β),4.13 (1H,m,H-2′),3.89 (3H,s,2-OMe),3.57 (2H,dd,J = 6.0,2.3 Hz,H-3′)；13C-NMR (150 MHz,CD3OD) δ: 127.7 (C-1),111.7 (C-2),150.6 (C-3),149.5 (C-4),116.5 (C-5),124.1 (C-6),147.0 (C-7),115.3 (C-8),169.2 (C-9),61.6 (C-1′),71.3 (C-2′),64.1 (C-3′)。以上数据与文献对照[8]后基本一致，故鉴定化合物1为1-O-阿魏酰甘油。
化合物2：黄色无定形粉末，ESI-MS m/z: 381.2 [M＋H]+，分子式C24H28O4。1H-NMR (600 MHz,CD3OD) δ: 6.98 (1H,s,H-7),6.13 (1H,dd,J = 17.4,10.6 Hz,H-24),6.12 (1H,s,H-10),6.11 (1H,s,H-4),6.05 (1H,s,H-2),5.28 (1H,d,J = 17.6 Hz,H-25α),5.21 (1H,d,J = 10.6 Hz,H-25β),3.35 (1H,m,H-6),3.25 (1H,m,H-5a),2.93 (1H,m,H-5b),2.71 (1H,m,H-14a),2.17 (1H,m,H-14b),1.97 (1H,m,H-13),1.42 (3H,s,H-20),1.36 (3H,s,H-23),1.35 (3H,s,H-22),1.34 (3H,s,H-19)；13C-NMR (150 MHz,CD3OD) δ: 21.4 (C-14),26.6 (C-20),26.9 (C-22),27.5 (C-23),27.6 (C-19),30.6 (C-6),33.5 (C-5),39.8 (C-13),41.1 (C-21),77.9 (C-12),100.9 (C-2),105.1 (C-10),107.4 (C-4),110.0 (C-25),113.3 (C-17),115.1 (C-15),126.3 (C-7),127.4 (C-8),137.2 (C-16),149.9 (C-24),154.3 (C-18),155.9 (C-9),156.3 (C-3),156.6 (C-1)。以上数据与文献对照[9]后基本一致，故鉴定化合物2为hypargystilbene A。
化合物3：白色粉末，ESI-MS m/z: 245.3 [M＋H]+，分子式C14H12O4。1H-NMR (600 MHz,CD3OD) δ: 7.34 (1H,d,J = 9.0 Hz,H-6′),7.28 (1H,d,J = 16.5 Hz,H-8),6.82 (1H,d,J = 16.5 Hz,H-7),6.46 (2H,d,J = 2.0 Hz,H-2,6),6.33 (1H,d,J = 2.0 Hz,H-3′),6.32 (1H,dd,J = 9.0,2.0 Hz,H-5′),6.15 (1H,d,J = 2.0 Hz,H-4)；13C-NMR (150 MHz,CD3OD) δ: 142.2 (C-1),105.6 (C-2,6),159.5 (C-3,5),102.3 (C-4),126.4 (C-7),124.8 (C-8),117.8 (C-1′),157.3 (C-2′),103.5 (C-3′),159.2 (C-4′),108.4 (C-5′),128.4 (C-6′)。以上数据与文献对照[10]后基本一致，故鉴定化合物3为氧化白藜芦醇。
化合物4：白色粉末，ESI-MS m/z: 261.1 [M＋H]+，分子式C14H12O5。1H-NMR (600 MHz,CD3OD) δ: 7.32 (1H,d,J = 8.4 Hz,H-β),6.92 (1H,s,H-6′),6.89 (1H,s,H-3′),6.80 (2H,d,J = 2.4 Hz,H-2,6),6.74 (1H,d,J = 8.4 Hz,H-α),6.30 (1H,s,H-4)；13C-NMR (150 MHz,CD3OD) δ: 98.4 (C-3′),102.3 (C-6′),103.5 (C-4),104.0 (C-2,6),113.2 (C-β),122.0 (C-α),123.0 (C-1′),133.8 (C-1),156.0 (C-2′),156.6 (C-4′),157.3 (C-5′),159.7 (C-3,5)。以上数据与文献对照[11]后基本一致，故鉴定化合物4为2′,3,4′,5,5′-五羟基-顺式-均二苯代乙烯。
化合物5：白色粉末，ESI-MS m/z: 229.1 [M＋H]+，分子式C14H12O3。1H-NMR (600 MHz,CD3OD) δ: 7.35 (2H,d,J = 8.1 Hz,H-2,6),6.96 (1H,d,J = 16.5 Hz,H-β),6.78 (1H,d,J = 16.5 Hz,H-α),6.76 (2H,d,J = 8.1 Hz,H-3′,5′),6.45 (2H,s,H-2′,6′),6.16 (1H,s,H-4)；13C-NMR (150 MHz,CD3OD) δ: 102.6 (C-4′),105.8 (C-2′,6′),116.5 (C-3,5),127.0 (C-α),128.8 (C-β),129.4 (C-2,6),130.4 (C-1),141.3 (C-1′),158.3 (C-4),159.6 (C-3′,5′)。以上数据与文献对照[12]后基本一致，故鉴定化合物5为白藜芦醇。
化合物6：浅黄色粉末，ESI-MS m/z: 183.1 [M＋H]+，分子式C9H10O4。1H-NMR (600 MHz,CD3OD) δ: 7.69 (1H,d,J = 8.8 Hz,H-6),6.35 (1H,dd,J = 8.8,2.3 Hz,H-5),6.30 (1H,d,J = 2.3 Hz,H-3),4.35 (2H,q,J = 7.1 Hz,H-8),1.36 (3H,t,J = 7.1 Hz,H-9)；13C-NMR (150 MHz,CD3OD) δ: 105.7 (C-1),165.0 (C-2),103.4 (C-3),165.6 (C-4),109.0 (C-5),132.6 (C-6),171.4 (C-7),62.0 (C-8),14.6 (C-9)。以上数据与文献对照[13]后基本一致，故鉴定为化合物6为2,4-二羟基苯甲酸乙酯。
化合物7：白色粉末，ESI-MS m/z: 183.3 [M＋H]+，分子式C9H10O4。1H-NMR (600 MHz,CD3OD) δ: 6.89 (1H,d,J = 2.1 Hz,H-2),6.84 (1H,dd,J = 8.4,2.1 Hz,H-6),6.32 (1H,d,J = 8.4 Hz,H-5),4.30 (2H,q,J = 7.1 Hz,H-8),1.35 (3H,t,J = 7.1 Hz,H-9)；13C-NMR (150 MHz,CD3OD) δ: 14.6 (C-9),61.7 (C-8),115.8 (C-2),117.4 (C-5),122.8 (C-1),123.5 (C-6),146.2 (C-3),151.5 (C-4),168.4 (C-7)。以上数据与文献对照[14]后基本一致，故鉴定化合物7为原儿茶酸乙酯。
化合物8：白色粉末，ESI-MS m/z: 163.1 [M＋H]+，分子式C9H6O3。1H-NMR (600 MHz,CD3OD) δ: 7.85 (1H,d,J = 9.6 Hz,H-4),7.45 (1H,d,J = 8.4 Hz,H-5),6.90 (1H,dd,J = 8.4,2.4 Hz,H-6),6.71 (1H,d,J = 2.4 Hz,H-8),6.18 (1H,d,J = 9.6 Hz,H-3)；13C-NMR (150 MHz,CD3OD) δ: 103.4 (C-8),112.3 (C-10),113.1 (C-3),114.6 (C-6),130.7 (C-5),146.1 (C-4),157.2 (C-9),163.2 (C-2),163.8 (C-7)。以上数据与文献对照[15]后基本一致，故鉴定化合物8为伞形花内酯。
化合物9：黄色粉末，ESI-MS m/z: 247.3 [M＋H]+，分子式C14H14O4。1H-NMR (600 MHz,CD3OD) δ: 7.76 (1H,d,J = 8.5 Hz,H-4),6.83 (1H,s,H-5),6.18 (1H,d,J = 8.5 Hz,H-3),5.27 (1H,t,J = 7.3 Hz,H-2″),3.52 (2H,d,J = 7.3 Hz,H-1″),1.85 (3H,s,H-4″),1.68 (3H,s,H-5″)；13C-NMR (150 MHz,CD3OD) δ: 164.6 (C-2),112.0 (C-3),146.5 (C-4),110.0 (C-5),143.8 (C-6),150.0 (C-7),117.2 (C-8),148.6 (C-9),112.5 (C-10),23.0 (C-1′),122.6 (C-2′),133.1 (C-3′),18.0 (C-4′),26.0 (C-5′)。以上数据与文献对照[16]后基本一致，故鉴定化合物9为8-(3,3-二甲基烯丙基)-6,7-二羟基香豆素。
化合物10：黄色粉末，ESI-MS m/z: 341.4 [M＋H]+，分子式C20H20O5。1H-NMR (600 MHz,CD3OD) δ: 8.10 (1H,d,J = 15.4 Hz,H-β),7.77 (1H,d,J = 8.9 Hz,H-6),7.73 (1H,d,J = 15.4 Hz,H-α),7.52 (1H,d,J = 8.5 Hz,H-6′),6.42 (1H,d,J = 8.9 Hz,H-5),6.38 (1H,dd,J = 8.5,2.3 Hz,H-5′),6.36 (1H,d,J = 2.3 Hz,H-3′),5.25 (1H,t,J = 7.3 Hz,H-2″),3.34 (2H,d,J = 14.5 Hz,H-1″),1.80 (3H,s,H-4″),1.68 (3H,s,H-5″)；13C-NMR (150 MHz,CD3OD) δ: 114.6 (C-1′),162.8 (C-2′),115.6 (C-3′),165.1 (C-4′),108.1 (C-5′),132.3 (C-6′),141.8 (C-α),117.8 (C-β),116.5 (C-1),160.8 (C-2),103.6 (C-3),162.8 (C-4),109.1 (C-5),130.2 (C-6),22.5 (C-1″),123.7 (C-2″),132.3 (C-3″),17.9 (C-4″),26.0 (C-5″)。以上数据与文献报道[17]一致，故鉴定化合物10为桑查耳酮A。
化合物11：黄色粉末，ESI-MS m/z: 301.2 [M－H]-，分子式C16H14O6。1H-NMR (600 MHz,CD3OD) δ: 7.25 (1H,d,J = 8.1 Hz,H-6′),6.36 (1H,dd,J = 8.1,2.3 Hz,H-5′),6.34 (1H,d,J = 2.3 Hz,H-3′),6.07 (1H,d,J = 2.3 Hz,H-6),6.04 (1H,d,J = 2.3 Hz,H-8),5.64 (1H,dd,J = 13.2,2.9 Hz,H-2),3.82 (3H,s,7-OMe),2.73 (2H,dd,J = 17.2,2.9 Hz,H-3ax),3.12 (2H,dd,J = 17.2,13.2 Hz,H-3eq)；13C-NMR (150 MHz,CD3OD) δ: 76.6 (C-2),43.1 (C-3),198.9 (C-4),165.2 (C-5),94.8 (C-6),169.4 (C-7),95.6 (C-8),165.2 (C-9),104.0 (C-10),56.6 (MeO-7),117.7 (C-1′),156.8 (C-2′),103.4 (C-3′),159.8 (C-4′),107.8 (C-5′),128.9 (C-6′)。以上数据与文献对照[18]后基本一致，故鉴定化合物11为桂木二氢黄素。
化合物12：黄色无定形粉末，ESI-MS m/z: 423.2 [M＋H]+，分子式C25H26O6。1H-NMR (600 MHz,CD3OD) δ: 7.56 (1H,d,J = 2.1 Hz,H-2′),7.49 (1H,dd,J = 8.3,2.1 Hz,H-6′),7.04 (1H,d,J = 8.3 Hz,H-5′),6.58 (1H,s,H-3),6.40 (1H,s,H-6),5.32 (1H,t,J = 6.8 Hz,H-2″),5.03 (1H,t,J = 6.8 Hz,H-6″),3.57 (2H,d,J = 6.8 Hz,H-1″),2.07 (2H,m,H-5″),1.98 (2H,m,H-4″),1.84 (3H,s,H-10″),1.55 (3H,s,H-8″),1.49 (3H,s,H-9″)；13C-NMR (150 MHz,CD3OD) δ: 165.2 (C-2),103.7 (C-3),183.4 (C-4),160.7 (C-5),99.2 (C-6),162.5 (C-7),107.4 (C-8),155.9 (C-9),105.1 (C-10),125.0 (C-1′),114.1 (C-2′),146.7 (C-3′),150.4 (C-4′),116.5 (C-5′),119.8 (C-6′),22.2 (C-1″),123.5 (C-2″),135.7 (C-3″),40.3 (C-4″),27.2 (C-5″) 123.7 (C-6″),131.6 (C-7″),17.6 (C-8″),25.7 (C-9″),16.5 (C-10″)。以上数据与文献对照[19]后基本一致，故鉴定化合物12为styracifolin C。
化合物13：浅黄色粉末，ESI-MS m/z: 423.2 [M＋H]+，分子式C25H26O6。1H-NMR (600 MHz,CD3OD) δ: 7.06 (1H,d,J = 8.3 Hz,H-6′),6.42 (1H,d,J = 2.2 Hz,H-3′),6.40 (1H,dd,J = 8.3,2.2 Hz,H-5′),6.32 (1H,s,H-8),5.26 (1H,t,J = 7.2 Hz,H-17),5.10 (1H,t,J = 7.0 Hz,H-12),3.35 (2H,d,J = 18.3 Hz,H-16),3.10 (2H,d,J = 7.0 Hz,H-11),1.80 (3H,s,H-20),1.69 (3H,s,H-19),1.60 (3H,s,H-15),1.40 (3H,s,H-14)；13C-NMR (150 MHz,CD3OD) δ: 163.2 (C-2),121.7 (C-3),183.6 (C-4),159.9 (C-5),112.4 (C-6),163.3 (C-7),93.6 (C-8),157.7 (C-9),105.2 (C-10),24.9 (C-11),122.9 (C-12),132 (C-13),25.9 (C-14),17.9 (C-15),22.3 (C-16),123.6 (C-17),131.9 (C-18),26.0 (C-19),17.6 (C-20),113.5 (C-1′),157.8 (C-2′),103.7 (C-3′),161.8 (C-4′),107.9 (C-5′),132.6 (C-6′)。以上数据与文献对照[20]后基本一致，故鉴定化合物13为柘树黄酮C。
化合物14：黄色油状物，ESI-MS m/z: 505.3 [M＋H]+，分子式C30H32O7。1H-NMR (600 MHz,CD3OD) δ: 3.33 (2H,d,J = 7.0 Hz,H-11),5.15 (1H,m,H-12),1.63 (3H,s,H-14),1.44 (3H,s,H-15),6.69 (1H,d,J = 10.0 Hz,H-16),5.67 (1H,d,J = 10.0 Hz,H-17),1.45 (6H,s,H-19,20),3.13 (2H,d,J = 7.0 Hz,H-1″),5.13 (1H,m,H-2″),1.45 (3H,s,H-4″),1.64 (3H,s,H-5″),6.71 (1H,s,H-3′),6.49 (1H,s,H-6′)；13C-NMR (150 MHz,CD3OD) δ: 163.4 (C-2),121.6 (C-3),184.2 (C-4),155.1 (C-5),105.9 (C-6),157.5 (C-7),108.5 (C-8),156.3 (C-9),105.8 (C-10),22.2 (C-11),123.2 (C-12),132.8 (C-13),18.0 (C-14),25.9 (C-15),116.7 (C-16),129.0 (C-17),78.7 (C-18),28.4 (C-19,20),112.0 (C-1′),149.8 (C-2′),104.6 (C-3′),150.1 (C-4′),139.3 (C-5′),117.4 (C-6′),24.9 (C-1″),122.8 (C-2″),132.2 (C-3″),25.9 (C-4″),17.6 (C-5″)。以上数据与文献对照[21]后基本一致，故鉴定化合物14为异叶波罗蜜素。
化合物15：黄色粉末，ESI-MS m/z: 503.2 [M＋H]+，分子式C30H30O7。1H-NMR (600 MHz,DMSO- d6) δ: 7.18 (1H,s,H-5′),6.65 (1H,d,J = 10.0 Hz,H-16),6.37 (1H,s,H-2′),6.11 (1H,d,J = 9.4 Hz,H-11),5.66 (1H,d,J = 10.0 Hz,H-17),5.46 (1H,d,J = 9.3 Hz,H-12),5.24 (1H,t,J = 6.6 Hz,H-2″),3.52 (1H,dd,J = 14.4,7.2 Hz,Hb-1″),3.46 (1H,dd,J = 14.2,6.8 Hz,Ha-1″),1.95 (3H,s,H-15),1.87 (3H,s,H-5″),1.71 (6H,s,H-19,20),1.46 (3H,s,H-14),1.45 (3H,s,H-4″)；13C-NMR (150 MHz,DMSO-d6) δ: 157.6 (C-2),109.0 (C-3),179.9 (C-4),154.8 (C-5),106.4 (C-6),157.5 (C-7),109.0 (C-8),155.4 (C-9),106.1 (C-10),71.3 (C-11),122.4 (C-12),139.6 (C-13),26.0 (C-14),18.7 (C-15),116.6 (C-16),129.2 (C-17),79.0 (C-18),28.5 (C-19),28.5 (C-20),22.3 (C-1″),123.3 (C-2″),132.7 (C-3″),25.9 (C-4″),18.3 (C-5″),107.9 (C-1′),153.2 (C-2′),105.5 (C-3′),152.6 (C-4′),142.0 (C-5′),110.0 (C-6′)。以上数据与文献对照[22-23]后基本一致，故鉴定化合物15为环异叶波罗蜜素。
化合物16：黄色粉末，ESI-MS m/z: 503.2 [M＋H]+，分子式C30H30O7。1H-NMR (600 MHz,CD3COCD3) δ: 6.77 (1H,d,J = 10.0 Hz,H-16),6.50 (1H,s,H-3′),5.82 (1H,d,J = 10.0 Hz,H-17),5.41 (1H,t,J = 6.7 Hz,H-2″),3.70,3.54 (各1H,dd,J = 14.0,8.0 Hz,H-1''),3.49,3.30 (各1H,dd,J = 15.0,7.0 Hz,H-11),2.45 (1H,t,J = 15 Hz,H-12),1.90 (3H,s,H-5″),1.75 (3H,s,H-15),1.72 (3H,s,H-4″),1.56 (3H,s,H-19,20),1.42 (3H,s,H-14)；13C-NMR (150 MHz,CD3COCD 3) δ: 162.3 (C-2),113.3 (C-3),182.5 (C-4),155.2 (C-5),106.6 ((C-6),157.8 (C-7),109.0 (C-8),156.0 (C-9),105.8 (C-10),21.2 (C-11),48.3 (C-12),94.5 (C-13),29.1 (C-14),23.7 (C-15),117.2 (C-16),129.7 (C-17),79.2 (C-18),29.1 (C-19),29.1 (C-20),22.8 (C-1″),124.4 (C-2″),132.4 (C-3″),26.7 (C-4″),19.0 (C-5″),106.0 (C-1′),152.3 (C-2′),106.0 (C-3′),147.8 (C-4′),138.7 (C-5′),134.5 (C-6′)。以上数据与文献对照[23]后基本一致，故鉴定化合物16为artonin A。
化合物17：黄色粉末，ESI-MS m/z: 503.2 [M＋H]+，分子式C30H30O7。1H-NMR (600 MHz,CD3OD) δ: 6.68 (1H,s,H-2′),6.67 (1H,d,J = 10.0 Hz,H-16),5.65 (1H,d,J = 10.0 Hz,H-17),5.27 (1H,m,H-2″),4.68,4.28 (各1H,s,H-15),3.96 (1H,d,J = 6.1 Hz,H-12),3.64,3.41 (各1H,dd,J = 14.0,8.0 Hz,H-1''),3.37 (1H,dd,J = 16.0,2.0 Hz,H-11α),2.43 (1H,dd,J = 16.0,7.0 Hz,H-11β),1.80 (6H,s,H-4″,5″),1.66 (3H,s,H-14),1.44 (各3H,s,H-19,20)；13C-NMR (150 MHz,CD3OD) δ: 162.4 (C-2),112.0 (C-3),182.1 (C-4),155.1 (C-5),106.1 (C-6),157.4 (C-7),109.1 (C-8),154.8 (C-9),109.1 (C-10),22.8 (C-11),38.6 (C-12),145.7 (C-13),22.0 (C-14),112.0 (C-15),116.8 (C-16),129.1 (C-17),78.6 (C-18),28.3 (C-19), 28.4 (C-20),107.2 (C-1′),152.4 (C-2′),105.5 (C-3′),152.0 (C-4′),136.7 (C-5′),130.6 (C-6′),22.3 (C-1″),124.0 (C-2″),132.0 (C-3″),26.0 (C-4″),18.2 (C-5″)。以上数据与文献对照[23]后基本一致，故鉴定化合物17为artonin B。
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