土木香根化学成分研究与土木香倍半萜内酯的结构修饰
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摘要
土木香(Inula helenium)又名祁木香、藏木香,为菊科旋覆花属多年生草本植物。广泛分布在欧洲、北美洲和亚洲东部,在我国东北、华北及西北地区有分布,在河北、山西、河南、湖北、四川等地有栽培。根茎常作药用,具有抗菌、抗炎、抗肿瘤、驱虫、降压等活性,可用于消化不良,胸腹胀痛,呕吐腹泻,痢疾等症[1]。其常见化学成分有倍半萜、倍半萜内酯、三萜、糖类、氨基酸类,其中倍半萜内酯以土木香内酯和异土木香内酯为主,为其特征性成分,也是土木香重要的活性成分。2005年,从土木香培养根中得到一个麝香草酚衍生物,生物活性试验表明其对金黄色葡萄球菌、粪肠球菌、大肠杆菌、铜绿假单胞菌、念球菌属等有中等的抑制活性,与异土木香内酯抑菌活性相似[2]。从土木香根分离得到的倍半萜内酯Isocostunolide对三种癌细胞(人黑素瘤细胞A20558,人肝细胞瘤HT-29,人结肠腺癌细胞HepG2)有明显的诱导性细胞毒性,其IC50分别是3.2,5.0,2.0μg/mL[3]。在对体外培养人肿瘤细胞增殖的影响试验中,异土木香内酯对U251SP和T-98 (人脑神经胶质瘤细胞株),HLE (人肝癌细胞株)MM1-CB和HMV-1 (人黑色素瘤细胞株),KT (人乳腺癌脑转移肿瘤细胞株)显示较强的抑制活性,并对移植性肿瘤(肝癌H22)具有明显的抑制作用,并呈现良好的剂量依赖关系[4]。2001年,Lawrence等对土木香内酯和异土木香内酯的α-氨基取代内酯的活性进行了研究,活性实验表明土木香内酯和异土木香内酯及其两类氨基取代内酯能明显诱导细胞凋亡[5]。因此寻找土木香中新的活性化合物,并进一步研究其同类化合物的结构与活性的关系,对土木香的研究开发具有重要意义。我们以土木香的根为研究对象,对其化学成分进行分离纯化和结构确定,并对部分化合物单体进行活性筛选。
目的:本研究旨在以土木香的根为研究对象,利用硅胶柱色谱、制备薄层色谱、高效液相色谱、葡聚糖凝胶色谱以及重结晶等分离纯化技术对其进行系统分离,寻找新的化学成分,并对提取的土木香倍半萜内酯进行结构修饰,分离纯化产物,并应用MS、1H-NMR、13C-NMR、1H-1H-COSY、HSQC、HMBC等现代化手段完成单体化合物分子的结构鉴定。
方法:干燥的土木香(Inula helenium)根切片(9.8 Kg)适当粉碎后,用95%乙醇连续冷浸提取三次,浸提物过滤,合并滤液减压浓缩至粘膏状(3.0 Kg),将1.5 Kg浸膏在搅拌下以石油醚超声提取,浓缩,继而得到石油醚部位(333.9 g),将石油醚提取过的浸膏悬浮于饱和食盐水,分别用二氯甲烷、乙酸乙酯和正丁醇萃取,浓缩,分别得到二氯甲烷部位(3.5 g)、乙酸乙酯部位(7.8 g)和正丁醇部位(34.7 g)。对提取得到的不同部位进行薄层检识并选择合适的洗脱剂进行硅胶柱色谱分离,以薄层硅胶色谱检识洗脱液成分,合并相同成分的洗脱液,利用硅胶柱色谱、聚酰胺柱色谱、葡聚糖凝胶色谱、制备薄层色谱、高效液相制备色谱以及重结晶等分离纯化技术对其进行系统研究,寻找新的化学成分,并应用MS、1H-NMR、13C-NMR、1H-1HCOSY、HSQC、HMBC、NOESY等现代波谱学方法对这些单体化合物进行检测,依据测定的图谱数据分析确定单体化合物的平面结构和立体结构。
选择合适的溶剂溶解土木香倍半萜内酯,在有催化剂存在的情况下分次加入反应剂,加热搅拌,间隔取样,以薄层色谱检识反应进行的情况。反应完全后回收溶剂,选择合适的洗脱剂对反应混合物进行分离纯化,并运用上述方法测定产物的结构。
结果:通过系统提取分离土木香(Inula helenium)的根的化学成分,从中分离得到8个单体化合物,并对其中5个进行结构鉴定,其中有2个倍半萜类化合物,2个甾体化合物,1个咖啡酸酸酐,分别为4, 4-dimethylsterols (2),Isoalantolactone (4),alantolactone (5),β-谷甾醇(6),Caffeic acid anhydride (7)。
结论:本课题对土木香(Inula helenium)根的化学成分进行了系统研究,具体采用了硅胶柱色谱、葡聚糖凝胶色谱、制备薄层色谱、高效液相色谱等多种分离手段或方法,共分离得到8个化合物,并且运用了多种现代波谱手段及其相关知识,对其中的5个化合物进行了结构鉴定。
Inula helenium, knowed as“qimuxiang”or“zangmuxiang”in traditional Chinese medicine, is a perennial herb of the Inula genus compositae family, grow wild in Europe, North America and the eastern part of Asia. It is distributed in northeast, northwest, and central region of China and cultivated in the province of Hebei, Shanxi, Henan, Hubei, Sichuan and so on. Dried roots of I. helenium have been traditionally used for dyspepsia, abdominal distention, vomiting, diarrhea, dysentery in traditional Chinese medicine. Extracts or the roots have been found to exhibit activity of anti-bacteria, antiinflammatory, anti-cancer, helminthicide and decompression. The common components of I. helenium were sesquiterpenes, sesquiterpene lactones, triterpenes, glycosides, amino acids. Among sesquiterpene lactones, alantolactone and isoalantolactone are the major and important active constitutent of I. helenium. In 2005, a thymol derivative was isolated from the I. helenium roots cultures and it showed moderate antimicrobial activity against Staphylococcus aureus, Enterococcus faecalis, Escherischia coli, Pseudomonas aeruginosa and Candida albicans, similar to the activities of isoalantolactone. Isocostunolide is a sesquiterpene lactone isolated from the roots of I. helenium, it was proved that could effectively induce cytotoxicity in three cancer cell lines of A2058, HT-29, and HepG2 with an IC50 of 3.2, 5.0 and 2.0μg/mL, respectively. In the anti-tumor activities of sesquiterpene lactone on the human tumor cell cultivated in vitro, isoalantolactone exhibited significant anti-growth activities to U251SP,HLE and MM1-CB and the portability tumor in mice and showed upstanding dose-dependent relationship. Lawrence et al. preceded a study onα-aminomethyl substituted lactone of alantolactone and isoalantolactone and all of the prepared compounds induced apoptosis and acted as an alkylating agents. It is interesting to find new active compounds and establish structure-activity relationship further for the research and development of I. helenium. In this experiment, we systemically investigated the chemical composition of the root of I. helenium, and established the structures of the isolated pure compounds on the basis of spectroscopic techniques including 1D and 2D NMR methods and bioactivity screening for part of monomer.
Objective: In order to develop the natural resources, enrich the diversities of traditional Chinese medicine and find out new compounds from the root of I. helenium, we use the technologies of Silica gel column chromatography, polyamide column chromatography, sephadex gel column chromatography, preparative TLC, HPLC and re-crystallization to systemically isolate and purify the compounds of this plant and prepare the constituents of the sesquiterpene lactone of the plant. Use the spectroscopic methods including MS, 1H-NMR, 13C-NMR, 1H-1H-COSY, HSQC and HMBC to characterize the structures of the isolated compounds. Besides, activities of several compounds were evaluated.
Methods: Lamellate dried roots of I. helenium (9.8 Kg) were extracted with 95% alcohol for three times and dipping fifteen days for one time. After filtered, the alcohol extract was concentrated in vacuum to yield the total crud extract of 3.0 Kg. The crud extract 1.5 Kg was re-extracted with petroleum ether in ultrasonic sound with perseverative agitation, concentrated and obtained the petroleum ether fraction 333.9 g. The remaining residue was suspended in saturated salt solution and re-extracted with dichloromethane, ethyl acetate and n-butanol in order. Three fractions were obtained: dichloromethane fraction 3.5 g, ethyl acetate fraction 7.8 g and n-butanol fraction 34.7g. The last fraction were applied to column chromatography for preliminary fractionation in turn, each fraction was monitored with TLC and combined the similar fractions together. Combined subfractions were subjected to Silica gel column chromatography, polyamide column chromatography, Sephadex gel column chromatography, preparative TLC for further separation and purification to get pure compounds. Spectroscopic methods including 1D and 2D NMR methods were used for the structural identification of these compounds.
Dissolve the sesquiterpene lactone in suitable solvent and add in the reactant fractional with the accelerant existed, heating and perseverative agitation and Check the progress with thin-layer chromatography. Retrieve solvent after the reaction finished and use the technologies of silica gel column chromatography to isolate and purify the admixture, characterize the structures of the synthetical compounds with the same methods mentioned above.
Results: Eight compounds were isolated from the roots of I. helenium, and five compounds were identified on the basis of chemical and spectral analysis: two sesquiterpenes, two sterides and one anhydride. They were 4, 4-dimethylsterols (2), isoalantolactone (4), alantolactone (5),β-sitosterol (6), caffeic acid anhydride (7).
Conclusion: Studies on the chemical components of the roots of I. helenium were practicable supported by our results. Application of silica gel column chromatography, polyamide column chromatography, sephadex gel column chromatography, preparative TLC in the studies and variety of spectroscopic methods were used to establish the structures of the compounds. We obtained 8 compounds in all, and the structures of 5 compounds were identified.
目的:本研究旨在以土木香的根为研究对象,利用硅胶柱色谱、制备薄层色谱、高效液相色谱、葡聚糖凝胶色谱以及重结晶等分离纯化技术对其进行系统分离,寻找新的化学成分,并对提取的土木香倍半萜内酯进行结构修饰,分离纯化产物,并应用MS、1H-NMR、13C-NMR、1H-1H-COSY、HSQC、HMBC等现代化手段完成单体化合物分子的结构鉴定。
方法:干燥的土木香(Inula helenium)根切片(9.8 Kg)适当粉碎后,用95%乙醇连续冷浸提取三次,浸提物过滤,合并滤液减压浓缩至粘膏状(3.0 Kg),将1.5 Kg浸膏在搅拌下以石油醚超声提取,浓缩,继而得到石油醚部位(333.9 g),将石油醚提取过的浸膏悬浮于饱和食盐水,分别用二氯甲烷、乙酸乙酯和正丁醇萃取,浓缩,分别得到二氯甲烷部位(3.5 g)、乙酸乙酯部位(7.8 g)和正丁醇部位(34.7 g)。对提取得到的不同部位进行薄层检识并选择合适的洗脱剂进行硅胶柱色谱分离,以薄层硅胶色谱检识洗脱液成分,合并相同成分的洗脱液,利用硅胶柱色谱、聚酰胺柱色谱、葡聚糖凝胶色谱、制备薄层色谱、高效液相制备色谱以及重结晶等分离纯化技术对其进行系统研究,寻找新的化学成分,并应用MS、1H-NMR、13C-NMR、1H-1HCOSY、HSQC、HMBC、NOESY等现代波谱学方法对这些单体化合物进行检测,依据测定的图谱数据分析确定单体化合物的平面结构和立体结构。
选择合适的溶剂溶解土木香倍半萜内酯,在有催化剂存在的情况下分次加入反应剂,加热搅拌,间隔取样,以薄层色谱检识反应进行的情况。反应完全后回收溶剂,选择合适的洗脱剂对反应混合物进行分离纯化,并运用上述方法测定产物的结构。
结果:通过系统提取分离土木香(Inula helenium)的根的化学成分,从中分离得到8个单体化合物,并对其中5个进行结构鉴定,其中有2个倍半萜类化合物,2个甾体化合物,1个咖啡酸酸酐,分别为4, 4-dimethylsterols (2),Isoalantolactone (4),alantolactone (5),β-谷甾醇(6),Caffeic acid anhydride (7)。
结论:本课题对土木香(Inula helenium)根的化学成分进行了系统研究,具体采用了硅胶柱色谱、葡聚糖凝胶色谱、制备薄层色谱、高效液相色谱等多种分离手段或方法,共分离得到8个化合物,并且运用了多种现代波谱手段及其相关知识,对其中的5个化合物进行了结构鉴定。
Inula helenium, knowed as“qimuxiang”or“zangmuxiang”in traditional Chinese medicine, is a perennial herb of the Inula genus compositae family, grow wild in Europe, North America and the eastern part of Asia. It is distributed in northeast, northwest, and central region of China and cultivated in the province of Hebei, Shanxi, Henan, Hubei, Sichuan and so on. Dried roots of I. helenium have been traditionally used for dyspepsia, abdominal distention, vomiting, diarrhea, dysentery in traditional Chinese medicine. Extracts or the roots have been found to exhibit activity of anti-bacteria, antiinflammatory, anti-cancer, helminthicide and decompression. The common components of I. helenium were sesquiterpenes, sesquiterpene lactones, triterpenes, glycosides, amino acids. Among sesquiterpene lactones, alantolactone and isoalantolactone are the major and important active constitutent of I. helenium. In 2005, a thymol derivative was isolated from the I. helenium roots cultures and it showed moderate antimicrobial activity against Staphylococcus aureus, Enterococcus faecalis, Escherischia coli, Pseudomonas aeruginosa and Candida albicans, similar to the activities of isoalantolactone. Isocostunolide is a sesquiterpene lactone isolated from the roots of I. helenium, it was proved that could effectively induce cytotoxicity in three cancer cell lines of A2058, HT-29, and HepG2 with an IC50 of 3.2, 5.0 and 2.0μg/mL, respectively. In the anti-tumor activities of sesquiterpene lactone on the human tumor cell cultivated in vitro, isoalantolactone exhibited significant anti-growth activities to U251SP,HLE and MM1-CB and the portability tumor in mice and showed upstanding dose-dependent relationship. Lawrence et al. preceded a study onα-aminomethyl substituted lactone of alantolactone and isoalantolactone and all of the prepared compounds induced apoptosis and acted as an alkylating agents. It is interesting to find new active compounds and establish structure-activity relationship further for the research and development of I. helenium. In this experiment, we systemically investigated the chemical composition of the root of I. helenium, and established the structures of the isolated pure compounds on the basis of spectroscopic techniques including 1D and 2D NMR methods and bioactivity screening for part of monomer.
Objective: In order to develop the natural resources, enrich the diversities of traditional Chinese medicine and find out new compounds from the root of I. helenium, we use the technologies of Silica gel column chromatography, polyamide column chromatography, sephadex gel column chromatography, preparative TLC, HPLC and re-crystallization to systemically isolate and purify the compounds of this plant and prepare the constituents of the sesquiterpene lactone of the plant. Use the spectroscopic methods including MS, 1H-NMR, 13C-NMR, 1H-1H-COSY, HSQC and HMBC to characterize the structures of the isolated compounds. Besides, activities of several compounds were evaluated.
Methods: Lamellate dried roots of I. helenium (9.8 Kg) were extracted with 95% alcohol for three times and dipping fifteen days for one time. After filtered, the alcohol extract was concentrated in vacuum to yield the total crud extract of 3.0 Kg. The crud extract 1.5 Kg was re-extracted with petroleum ether in ultrasonic sound with perseverative agitation, concentrated and obtained the petroleum ether fraction 333.9 g. The remaining residue was suspended in saturated salt solution and re-extracted with dichloromethane, ethyl acetate and n-butanol in order. Three fractions were obtained: dichloromethane fraction 3.5 g, ethyl acetate fraction 7.8 g and n-butanol fraction 34.7g. The last fraction were applied to column chromatography for preliminary fractionation in turn, each fraction was monitored with TLC and combined the similar fractions together. Combined subfractions were subjected to Silica gel column chromatography, polyamide column chromatography, Sephadex gel column chromatography, preparative TLC for further separation and purification to get pure compounds. Spectroscopic methods including 1D and 2D NMR methods were used for the structural identification of these compounds.
Dissolve the sesquiterpene lactone in suitable solvent and add in the reactant fractional with the accelerant existed, heating and perseverative agitation and Check the progress with thin-layer chromatography. Retrieve solvent after the reaction finished and use the technologies of silica gel column chromatography to isolate and purify the admixture, characterize the structures of the synthetical compounds with the same methods mentioned above.
Results: Eight compounds were isolated from the roots of I. helenium, and five compounds were identified on the basis of chemical and spectral analysis: two sesquiterpenes, two sterides and one anhydride. They were 4, 4-dimethylsterols (2), isoalantolactone (4), alantolactone (5),β-sitosterol (6), caffeic acid anhydride (7).
Conclusion: Studies on the chemical components of the roots of I. helenium were practicable supported by our results. Application of silica gel column chromatography, polyamide column chromatography, sephadex gel column chromatography, preparative TLC in the studies and variety of spectroscopic methods were used to establish the structures of the compounds. We obtained 8 compounds in all, and the structures of 5 compounds were identified.
引文
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24 Kalauni SK, Awale S, Tezuka Y, et al. Cassane- and norcassane-typediterpenes of caesalpinia crista from myanmar. J. Nat. Prod., 2004, 67: 1859-1863
25 Ragasa CY, Hofilen JG, Rideout JA. New furanoid diterpenes from caesalpinia pulcherrima. J. Nat. Prod, 2002, 65: 1107-1110
26 Cheenpracha S, Srisuwan R, Karalai C, et al. New diterpenoids from stems and roots of caesalpinia crista. Tetrahedron, 2005, 61: 8656-8662
27 Dickson RA, Houghton PJ, Hylands PJ. Antibacterial and antioxidant cassane diterpenoids from caesalpinia benthamiana. Phytochemistry, 2007, 68: 1436-1441
28 Yodsaoue O, Cheenpracha S, Karalai C, et al. Phanginin A-K, diterpenoids from the seeds of caesalpinia sappan Linn. Phytochemistry, 2008, 69: 1242-1249
29 Yadav PP, Maurya R, Sarkar J, et al. Cassane diterpenes from caesalpinia bonduc. Phytochemistry, 2009, 70: 256-261
30 Kinoshita T. Chemical studies on the philippine crude drug calumbibit (seeds of caesalpinia bonduc): the isolation of new cassane diterpenes fused withα,β-butenolide. Chem. Pharm. Bull, 2000, 48: 1375-1377
31 Jiang RW, Ma SC, But PPH, et al. Isolation and characterization of spirocaesalmin, a novel rearranged vouacapane diterpenoid from caesalpinia minax hance. J. Chem. Soc. Perkin Trans, 2001, 1: 2920-2923
32 Kinoshita T, Haga Y, Narimatsu S, et al. The isolation and structure elucidation of new cassane diterpene-acids from caesalpinia crista L. (fabaceae), and review on the nomenclature of some caesalpinia species. Chem. Pharm. Bull, 2005, 53: 717-720
33 Yadav PP, Arora A, Bid HK, et al. New cassane butenolide hemiketal diterpenes from the marine creeper caesalpinia bonduc and their antiproliferative activity. Tetrahedron Letters, 2007, 48: 7194-7198
34 Wu ZH, Wang YY, Huang J, et al. A new cassane diterpene from caesalpinia bonduc (fabaceae). Asian Journal of Traditional Medicines, 2007, 2: 135-139
35 Wu ZH, Wang LB, Gao HY, et al. Neocaesalpin L1 , a new diterpenoidcompound from caesalpinia minax. China Journal of Chinese Materia Medica, 2008, 33: 1145-1147
36 Cheng Y, Ma LY, Miao JH, et al. A new cassane diterpenoid lactone from the seed of caesalpinia minax. Chinese Chemical Letters, 2009, 22: 444-446
37 Kiem PV, Minh CV, Huong HT, et al. Caesaldecan, a cassane diterpenoid from the leaves of caesalpinia decapetala. Chem. Pharm. Bull, 2005, 53: 428-430
38 Mclean S, Reynods WF, Tay LL. Caesalpinin, a rearranged cassane furanoditerpene of caesalpinia bonducella. Tetrahedron letters, 1997, 38: 5767-5770
39 Wu ZH. Studies on the chemical constituents from seeds of caesalpinina minax hance. School of Traditional Chi nese Materia Medica, Shenyang Pharmaceutical University. 2008
40 Wu ZH. A novel diterpene from caesalpinia minax. Chinese Traditional and Herbal Drugs, 2008, 39: 1127-1129
41 Yuan JQ, Zou ZJ, Yang XZ, et al. Studies on the chemical constituents from seeds of caesalpinina minax hance. Chin. J. Pharm. Anal, 2008, 28: 1489-1493
42 Banskota AH, Attamimi F, Usia T, et al. Novel norcassane-type diterpene from the seed kernels of caesalpinia crista. Tetrahedron Letters, 2003, 44: 6879-6882
43 Wu ZH, Wan LB, Gao HY, et al. New diterpene from the seeds of caesalpinia minax hance. Journal of Shenyang Pharmaceutical University. 2008, 25: 96-966
44 Woldemichae GM, Singh MP, Maiese WM, et al. Constituents of antibacterial extract of caesalpinia paraguariensis. burk. Z. Naturforsch, 2003, 58: 70-75
45 Vasconcelos JF, Teixeira MM, et al. The triterpenoid lupeol attenuates allergic airway inflammation in a murine model. International Immunopharmacology, 2008, 8: 1216-1221
46 Chen P. Studies on the chemical cinstituents of caesalpinina millettii hook. et arn. livistona chinensis (jacq.) R. Br and souliea vaginata (maxim.) franch. Institute of medicinal plant development, chinese academy of medical sciences and peking union medical college, beijing. 2007
47 Mcpherson DD, Cordell GA, Soejarto DD, et al. Peltogynoids and homoisoflavonoids from caesalpinia pulcherrima. Phytochemistry, 1983, 22: 2835-3838
48 Srinivas KVNS, Rao YK, Mahender I, et al. Flavanoids from caesalpinia pulcherrima. Phytochemistry, 2003, 63: 789-793
49 Zhao P, Iwamoto Y, Kouno I, et al. Stimulating the production of homoisoflavonoids in cell suspension cultures of caesalpinia pulcherrima using cork tissue. Phytochemistry, 2004, 65: 2455-2461
50 Rao YK, Fang SH, Tzeng YM. Anti-inflammatory activities of flavonoids isolated from caesalpinia pulcherrima. Journal of Ethnopharmacology, 2005, 100: 249-253
51 Namikoshi M, Nakata H, Saitoh T. Homoisoflavonoids from caesalpinia sappan. Phytochemistry, 1987, 26: 1831-1833
52 Namikoshi M, Nakata H, Yamada H, et al. Homoisoflavonoids and related compoundsⅡ, isolation and absolute configurations of 3, 4-dihydroxylated homoisoflavans and brazileins from caesalpinina sappan L. Chem. Pharm. Bull, 1987, 35: 2761-2773
53 Nguyen MTT, Awale S, Tezuka Y, et al. Xanthine oxidase inhibitors from the heartwood of vietnamese caesalpinia sappan. Chem. Pharm. Bull, 2005, 53: 984-988
54 Namikoshi M, Saitoh T. Homoisoflavonoids and related compounds.Ⅳ. absolute configurations of homoisoflavonoids from caesalpinia sappan L. Chem. Pharm. Bull, 1987, 35: 3597-3602
55 Jeong GS, Lee DS, Kwon TO, et al. Cytoprotective constituents of the heartwood of caesalpinia sappan on glutamate-induced oxidative damage in HT22 cells. Biol. Pharm. Bull, 2009, 32: 945-949
56 Fu LC, Huang XA, Lai ZY, et al. A new 3-benzylchroman derivative from sappan lignum (caesalpinia sappan). Molecules, 2008, 13: 1923-1930
57 Washiyama M, Sasaki Y, Hosokawa T, et al. Anti-inflammatory constituents of sappan lignum. Biol. Pharm. Bull, 2009, 32: 941-944
58 Ata A, Gale EM, Samarasekera R, Bioactive chemical constituents of caesalpinia bonduc (fabaceae). Phytochemistry Letters, 2009, 2: 106-109
59 Xie YW, Ming DS, Xu HX, et al. Vasorelaxing effects of caesalpinia sappan involvement of endogenous nitric oxide. Life Science, 2000, 67: 1913-1918
60 Ye M, Xie WD, Lei F, et al. Brazilein, an important immunosuppressive component from caesalpinia sappan L. International Immunopharmacology, 2006, 6: 426-432
61 Hu J, Yan XL, Wang W, et al. Antioxidant activity in vitro of three constituents from caesalpinia sappan L. Tsinghua Science and Technology, 2008, 13: 474-479
62 Yang BO, Ke CQ, He ZS, et al. Brazilide A, a novel lactone with an unprecedented skeleton from caesalpinia sappan. Tetrahedron Letters, 2002, 43: 1731-1733
63 Reddy VLN, Ravikanth V, Lakshmi VVNSJ, et al. Inhibitory activity of homoisoflavonoids from caesalpinia sappan against beauveria bassiana. Fitoterapia, 2003, 74: 600-602
64 Shimokawa T, kinjo J, Yamahara J, et al. Two novel aromatoc compounds from caesalpinin sappan. Chem. Pharm. Bull, 1985, 33: 3545-3547
65 Safitri R, Tarigan P, Freisleben HJ. Antioxidant activity in vitro of two aromaticcompounds from caesalpinia sappan L. Biofactors, 2003, 19: 71-77
66 Nagai M, Nagumo S, Protosappanins E-1 and E-2, stereoisomeric dibenzoxocins combined with brazilin from sappan Lignum. Chem. Pharm. Bull, 1990, 38, 1490-1494
67 Nguyen MTT, Awale S, Tezuka Y, et al. Neosappanone A, a xanthine oxidase (XO) inhibitory dimeric methanodi benzoxocinone with a new carbon skeleton from caesalpinia sappan. Tetrahedron Letters, 2004, 45: 8519-8522
68 Srinivasan R, Chandrasekar MJN, Nanjan MJ, et al. Antioxidant activity of caesalpinia digyna root. Journal of Ethnopharmacology, 2007, 113: 284-291
69 Nozaki H, Hayashi KI, Kido M, et al. Pauferrol A, a novel chalcone trimer with a cyclobutane ring from caesalpinia ferrea mart exhibiting DNA topoisomerase II inhibition and apoptosis-inducing activity. Tetrahedron Letters. 2007, 48: 8290-8292
70 Zhang Q, Liu XT, Liang JY, et al. Chemical constituents from the stem of caesalpinia decapetala. Chin. J. Nat. Med, 2008, 6: 168-172
71 Kondo K, Takaishi Y, Shibata H, et al. ILSMRs (intensifier ofβ-lactam-susceptibility in methicillin-resistant Staphylococcus aureus) from tara [caesalpinia spinosa (molina) kuntze]. Phytomedicine, 2006, 13: 209-212
72 Nakamura ES, Kurosaki F, Arisawa M, et al. Cancer chemopreventive effects of constituents of caesalpinia ferrea and related compounds. Cancer Letters, 2002, 177: 119-124
73 Ueda H, Tachibana Y, Moriyasu M, et al. Aldose reductase inhibitors from the fruits of caesalpinia ferrea mart. Phytomedicine, 2001, 8: 377-381
74 Mendes CC, Bahia MV, David, JM, et al. Constituents of caesalpinia pyramidalis. Fitoterapia, 2000, 71: 205-207
75 Lim MY, Jeon JH, Jeong EY, et al. Antimicrobial activity of 5-hydroxy-1, 4-naphthoquinone isolated from caesalpinia sappan toward intestinal bacteria. Food Chemistry, 2007, 100: 1254-1258
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3 Jiang RW, But PPH, Ma SC, et al. Structure and antiviral properties of macrocaesalmin, a novel cassane furanoditerpenoid lactone from the seeds of caesalpinia minax hance. Tetrahedron Letters, 2002, 43: 2415-2418
4 Mcpherson DD, Che CT, Cordell GA, et al. Diterpenoids from caesalpinia pulcherrima. Phytochemistry, 1986, 25: 167-170
5 Roach JS, McLean S, Reynolds WF, et al. Cassane diterpenoids of caesalpinia pulcherrima. J. Nat. Prod, 2003, 66: 1378-1381
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8 Jiang RW, But PPH, Ma SC, et al. Furanoditerpenoid lactones from the seeds of caesalpinia minax hance. Phytochemistry, 2001, 57: 517–521
9 Ogawa K, Aoki I, Sashida Y, et al. Caesaljapin, a cassane diterpenoid from caesalpinia decapetala var. Japonica. Phytochemistry, 1992. 31: 2897-2898
10 Kitagawa I, Simanjuntak P, Manmud T, et al. Indonesian medicinal plants.Ⅷ. chemical structures of caesaldekarins c, d, and e, three additional cassane-type furanoditerpenes from the roots of caesalpinina major (fabaceae). several interesting reaction products of caesaldekarin a provided by n-bromosuccinimide treatment. Chem. Pharm. Bull, 1996, 44: 1157-1161
11 Kalauni SK, Awale S, Tezuka Y, et al. New cassane-type diterpenes of caesalpinia crista from myanmar. Chem. Pharm. Bull, 2005, 53: 214-218
12 Kalauni SKK, Awale S, Tezuka Y, et al. Methyl migrated cassane-typefuranoditerpenes of caesalpinia crista from myanmar. Chem. Pharm. Bull, 2005, 53: 1300-1304
13 Peter SR, Tinto WF, Bonducellpins A-D, new cassane furanoditerpenes of caesalpinia bonduc. J. Nat. Prod, 1997, 60: 1219-1221
14 Awale S, Linn TZ, Tezuka Y, et al. Constituents of caesalpinina crista from indonesia. Chem. Pharm. Bull, 2006, 54: 213-218
15 Patil AD, Freyer AJ, Web RL, et al. Pulcherrimins A-D, novel diterpene dibenzoates from caesalpiniu pulcherrima with selective activity against DNA repair-deficient yeast mutants. Tetrahedron, 1997, 53: 1583-1592
16 Lyder DL, Peter SR, Tinto WF, et al. Minor cassane diterpenoids of caesalpinia bonduc. J. Nat. Prod, 1998, 61, 1462-1465
17 Ragasa CY, Ganzon J, HOFILE?A J, et al. A new furanoid diterpene from caesalpinia pulcherrima. Chem. Pharm. Bull, 2003, 51: 1208-1210
18 Peter S, Tinto WF, Mclean S, et al. Cassane diterpenes from caesalpinia bonducella. Phytochemistry, 1998, 47: 1153-1155
19 Shu SH. Studies on the chemical constituents of caesalpinina sappan and bridelia tomentosa. Institute of medicinal plant development, chinese academy of medical sciences and peking union medical college, beijing. 2007
20 Udenigwe CC, Ata A, Samarasekera R. Glutathione s-transferase inhibiting chemical constituents of caesalpinia bonduc. Chem. Pharm. Bull, 2007, 55: 442-445
21 Roengsumran S, Limsuwankesorn S, Ngamrojnavanich N, et al. Cassane diterpenoid from caesalpinia major. Phytochemistry, 2000, 53: 841-844
22 Jiang RW, Ma SC, But PPH, et al. New antiviral cassane furano- diterpenes from caesalpinia minax. J. Nat. Prod., 2001, 64: 1266-1272
23 Jiang RW, Ma SC, He ZD, et al. Molecular structures and antiviral activities of naturally occurring and modified cassane furanoditerpenoids and friedelane triterpenoids from caesalpinia minax. Bioorganic & Medicinal Chemistry, 2002, 10: 2161-2170
24 Kalauni SK, Awale S, Tezuka Y, et al. Cassane- and norcassane-typediterpenes of caesalpinia crista from myanmar. J. Nat. Prod., 2004, 67: 1859-1863
25 Ragasa CY, Hofilen JG, Rideout JA. New furanoid diterpenes from caesalpinia pulcherrima. J. Nat. Prod, 2002, 65: 1107-1110
26 Cheenpracha S, Srisuwan R, Karalai C, et al. New diterpenoids from stems and roots of caesalpinia crista. Tetrahedron, 2005, 61: 8656-8662
27 Dickson RA, Houghton PJ, Hylands PJ. Antibacterial and antioxidant cassane diterpenoids from caesalpinia benthamiana. Phytochemistry, 2007, 68: 1436-1441
28 Yodsaoue O, Cheenpracha S, Karalai C, et al. Phanginin A-K, diterpenoids from the seeds of caesalpinia sappan Linn. Phytochemistry, 2008, 69: 1242-1249
29 Yadav PP, Maurya R, Sarkar J, et al. Cassane diterpenes from caesalpinia bonduc. Phytochemistry, 2009, 70: 256-261
30 Kinoshita T. Chemical studies on the philippine crude drug calumbibit (seeds of caesalpinia bonduc): the isolation of new cassane diterpenes fused withα,β-butenolide. Chem. Pharm. Bull, 2000, 48: 1375-1377
31 Jiang RW, Ma SC, But PPH, et al. Isolation and characterization of spirocaesalmin, a novel rearranged vouacapane diterpenoid from caesalpinia minax hance. J. Chem. Soc. Perkin Trans, 2001, 1: 2920-2923
32 Kinoshita T, Haga Y, Narimatsu S, et al. The isolation and structure elucidation of new cassane diterpene-acids from caesalpinia crista L. (fabaceae), and review on the nomenclature of some caesalpinia species. Chem. Pharm. Bull, 2005, 53: 717-720
33 Yadav PP, Arora A, Bid HK, et al. New cassane butenolide hemiketal diterpenes from the marine creeper caesalpinia bonduc and their antiproliferative activity. Tetrahedron Letters, 2007, 48: 7194-7198
34 Wu ZH, Wang YY, Huang J, et al. A new cassane diterpene from caesalpinia bonduc (fabaceae). Asian Journal of Traditional Medicines, 2007, 2: 135-139
35 Wu ZH, Wang LB, Gao HY, et al. Neocaesalpin L1 , a new diterpenoidcompound from caesalpinia minax. China Journal of Chinese Materia Medica, 2008, 33: 1145-1147
36 Cheng Y, Ma LY, Miao JH, et al. A new cassane diterpenoid lactone from the seed of caesalpinia minax. Chinese Chemical Letters, 2009, 22: 444-446
37 Kiem PV, Minh CV, Huong HT, et al. Caesaldecan, a cassane diterpenoid from the leaves of caesalpinia decapetala. Chem. Pharm. Bull, 2005, 53: 428-430
38 Mclean S, Reynods WF, Tay LL. Caesalpinin, a rearranged cassane furanoditerpene of caesalpinia bonducella. Tetrahedron letters, 1997, 38: 5767-5770
39 Wu ZH. Studies on the chemical constituents from seeds of caesalpinina minax hance. School of Traditional Chi nese Materia Medica, Shenyang Pharmaceutical University. 2008
40 Wu ZH. A novel diterpene from caesalpinia minax. Chinese Traditional and Herbal Drugs, 2008, 39: 1127-1129
41 Yuan JQ, Zou ZJ, Yang XZ, et al. Studies on the chemical constituents from seeds of caesalpinina minax hance. Chin. J. Pharm. Anal, 2008, 28: 1489-1493
42 Banskota AH, Attamimi F, Usia T, et al. Novel norcassane-type diterpene from the seed kernels of caesalpinia crista. Tetrahedron Letters, 2003, 44: 6879-6882
43 Wu ZH, Wan LB, Gao HY, et al. New diterpene from the seeds of caesalpinia minax hance. Journal of Shenyang Pharmaceutical University. 2008, 25: 96-966
44 Woldemichae GM, Singh MP, Maiese WM, et al. Constituents of antibacterial extract of caesalpinia paraguariensis. burk. Z. Naturforsch, 2003, 58: 70-75
45 Vasconcelos JF, Teixeira MM, et al. The triterpenoid lupeol attenuates allergic airway inflammation in a murine model. International Immunopharmacology, 2008, 8: 1216-1221
46 Chen P. Studies on the chemical cinstituents of caesalpinina millettii hook. et arn. livistona chinensis (jacq.) R. Br and souliea vaginata (maxim.) franch. Institute of medicinal plant development, chinese academy of medical sciences and peking union medical college, beijing. 2007
47 Mcpherson DD, Cordell GA, Soejarto DD, et al. Peltogynoids and homoisoflavonoids from caesalpinia pulcherrima. Phytochemistry, 1983, 22: 2835-3838
48 Srinivas KVNS, Rao YK, Mahender I, et al. Flavanoids from caesalpinia pulcherrima. Phytochemistry, 2003, 63: 789-793
49 Zhao P, Iwamoto Y, Kouno I, et al. Stimulating the production of homoisoflavonoids in cell suspension cultures of caesalpinia pulcherrima using cork tissue. Phytochemistry, 2004, 65: 2455-2461
50 Rao YK, Fang SH, Tzeng YM. Anti-inflammatory activities of flavonoids isolated from caesalpinia pulcherrima. Journal of Ethnopharmacology, 2005, 100: 249-253
51 Namikoshi M, Nakata H, Saitoh T. Homoisoflavonoids from caesalpinia sappan. Phytochemistry, 1987, 26: 1831-1833
52 Namikoshi M, Nakata H, Yamada H, et al. Homoisoflavonoids and related compoundsⅡ, isolation and absolute configurations of 3, 4-dihydroxylated homoisoflavans and brazileins from caesalpinina sappan L. Chem. Pharm. Bull, 1987, 35: 2761-2773
53 Nguyen MTT, Awale S, Tezuka Y, et al. Xanthine oxidase inhibitors from the heartwood of vietnamese caesalpinia sappan. Chem. Pharm. Bull, 2005, 53: 984-988
54 Namikoshi M, Saitoh T. Homoisoflavonoids and related compounds.Ⅳ. absolute configurations of homoisoflavonoids from caesalpinia sappan L. Chem. Pharm. Bull, 1987, 35: 3597-3602
55 Jeong GS, Lee DS, Kwon TO, et al. Cytoprotective constituents of the heartwood of caesalpinia sappan on glutamate-induced oxidative damage in HT22 cells. Biol. Pharm. Bull, 2009, 32: 945-949
56 Fu LC, Huang XA, Lai ZY, et al. A new 3-benzylchroman derivative from sappan lignum (caesalpinia sappan). Molecules, 2008, 13: 1923-1930
57 Washiyama M, Sasaki Y, Hosokawa T, et al. Anti-inflammatory constituents of sappan lignum. Biol. Pharm. Bull, 2009, 32: 941-944
58 Ata A, Gale EM, Samarasekera R, Bioactive chemical constituents of caesalpinia bonduc (fabaceae). Phytochemistry Letters, 2009, 2: 106-109
59 Xie YW, Ming DS, Xu HX, et al. Vasorelaxing effects of caesalpinia sappan involvement of endogenous nitric oxide. Life Science, 2000, 67: 1913-1918
60 Ye M, Xie WD, Lei F, et al. Brazilein, an important immunosuppressive component from caesalpinia sappan L. International Immunopharmacology, 2006, 6: 426-432
61 Hu J, Yan XL, Wang W, et al. Antioxidant activity in vitro of three constituents from caesalpinia sappan L. Tsinghua Science and Technology, 2008, 13: 474-479
62 Yang BO, Ke CQ, He ZS, et al. Brazilide A, a novel lactone with an unprecedented skeleton from caesalpinia sappan. Tetrahedron Letters, 2002, 43: 1731-1733
63 Reddy VLN, Ravikanth V, Lakshmi VVNSJ, et al. Inhibitory activity of homoisoflavonoids from caesalpinia sappan against beauveria bassiana. Fitoterapia, 2003, 74: 600-602
64 Shimokawa T, kinjo J, Yamahara J, et al. Two novel aromatoc compounds from caesalpinin sappan. Chem. Pharm. Bull, 1985, 33: 3545-3547
65 Safitri R, Tarigan P, Freisleben HJ. Antioxidant activity in vitro of two aromaticcompounds from caesalpinia sappan L. Biofactors, 2003, 19: 71-77
66 Nagai M, Nagumo S, Protosappanins E-1 and E-2, stereoisomeric dibenzoxocins combined with brazilin from sappan Lignum. Chem. Pharm. Bull, 1990, 38, 1490-1494
67 Nguyen MTT, Awale S, Tezuka Y, et al. Neosappanone A, a xanthine oxidase (XO) inhibitory dimeric methanodi benzoxocinone with a new carbon skeleton from caesalpinia sappan. Tetrahedron Letters, 2004, 45: 8519-8522
68 Srinivasan R, Chandrasekar MJN, Nanjan MJ, et al. Antioxidant activity of caesalpinia digyna root. Journal of Ethnopharmacology, 2007, 113: 284-291
69 Nozaki H, Hayashi KI, Kido M, et al. Pauferrol A, a novel chalcone trimer with a cyclobutane ring from caesalpinia ferrea mart exhibiting DNA topoisomerase II inhibition and apoptosis-inducing activity. Tetrahedron Letters. 2007, 48: 8290-8292
70 Zhang Q, Liu XT, Liang JY, et al. Chemical constituents from the stem of caesalpinia decapetala. Chin. J. Nat. Med, 2008, 6: 168-172
71 Kondo K, Takaishi Y, Shibata H, et al. ILSMRs (intensifier ofβ-lactam-susceptibility in methicillin-resistant Staphylococcus aureus) from tara [caesalpinia spinosa (molina) kuntze]. Phytomedicine, 2006, 13: 209-212
72 Nakamura ES, Kurosaki F, Arisawa M, et al. Cancer chemopreventive effects of constituents of caesalpinia ferrea and related compounds. Cancer Letters, 2002, 177: 119-124
73 Ueda H, Tachibana Y, Moriyasu M, et al. Aldose reductase inhibitors from the fruits of caesalpinia ferrea mart. Phytomedicine, 2001, 8: 377-381
74 Mendes CC, Bahia MV, David, JM, et al. Constituents of caesalpinia pyramidalis. Fitoterapia, 2000, 71: 205-207
75 Lim MY, Jeon JH, Jeong EY, et al. Antimicrobial activity of 5-hydroxy-1, 4-naphthoquinone isolated from caesalpinia sappan toward intestinal bacteria. Food Chemistry, 2007, 100: 1254-1258