怀槐化学成分的研究
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摘要
怀槐Maackia amurensis Rupr. et Maxim.,又名山槐、高丽槐、朝鲜槐，是豆科(Leguminosae)马鞍树属(Maackia)植物。怀槐具有抗氧化、抗辐射、抗肿瘤及抗炎等作用，民间用来治疗跌打损伤、瘀血肿痛、风湿性关节炎、溃疡等症。
本论文对怀槐树皮70％乙醇提取物的乙酸乙酯萃取部分进行化学成分的研究，经反复硅胶柱色谱，Sephadex LH-20和重结晶等手段从怀槐中分离得到17个化合物，根据化合物的理化性质、波谱数据及与对照品和文献数据对照鉴定了其中14个化合物的化学结构，分别为：鸢尾种苷元(MAE2, tektorigenin)、染料木素(MAE3, genistein)、阿夫罗摩辛(MAE4, afromosin)、樱黄素(MAE5, prunetin)、芒柄花黄素(MAE6,formononetin)、ononin 6"-O-acetate(MAE7)、maackiaflavanone(MAE8)、maackiain3-O-(6'-O-malonyl-β-D-glucopyranoside)(MAE10)、maackiain 3-O(6'-O-acetyl-β-D-glucopyranoside)(MAE11)、di-O-methyldaidzein(MAE12)、maackiain(MAE13)、β-谷甾醇(MAE15，β-sitoterol)、鸢尾种苷(MAE16，tectoridin)和afromosin 7-O-β-D-glucopyranoside(MAE17)。
其中化合物MAE5、7、10和11均为首次从该属植物中分离得到，化合物MAE8、12和13均为首次从该植物中分离得到。
Maackia amurensis Rupr. et Maxim., the plant of Leguminosae, has the antioxidant, antiradical, antitumour and anti-inflammation activities, being used to treat injuries from falls, bruise and gall, rheumatoid arthritis, ulcer and so on.
Seventeen compounds were separated from the EtOAc fraction of 70% ethanol extraction of M. amurensis by repeated silica gel column chromatography, Sephadex LH-20 column chromatography, recrystallization and so on.
Fourteen compounds' structures were identified on the basis of their physico-chemical properties and spectroscopic analysis. The compounds are shown as follows: tectorigenin(MAE2), genistein (MAE3), afromosin(MAE4), prunetin(MAE5), formononetin (MAE6), ononin 6"-O-acetate (MAE7), maackiaflavanone (MAE8), maackiain 3-O(6'-O-malonyl-β-D-glucopyranoside) (MAE10), maackiain 3-O-(6'-O-acetyl-β-D-glucopyranoside) (MAE11), di-O-methyldaidzein(MAE12), maackiain (MAE13), β-sitosterol (MAE15), tectoridin (MAE16) and afromosin 7-O-β-D-glucopyranoside (MAE17). Compounds MAE5, 7, 10 and 11 were isolated from this genus for the first time, and compounds MAE8, 12 and 13 were isolated from this species for the first time.
本论文对怀槐树皮70％乙醇提取物的乙酸乙酯萃取部分进行化学成分的研究，经反复硅胶柱色谱，Sephadex LH-20和重结晶等手段从怀槐中分离得到17个化合物，根据化合物的理化性质、波谱数据及与对照品和文献数据对照鉴定了其中14个化合物的化学结构，分别为：鸢尾种苷元(MAE2, tektorigenin)、染料木素(MAE3, genistein)、阿夫罗摩辛(MAE4, afromosin)、樱黄素(MAE5, prunetin)、芒柄花黄素(MAE6,formononetin)、ononin 6"-O-acetate(MAE7)、maackiaflavanone(MAE8)、maackiain3-O-(6'-O-malonyl-β-D-glucopyranoside)(MAE10)、maackiain 3-O(6'-O-acetyl-β-D-glucopyranoside)(MAE11)、di-O-methyldaidzein(MAE12)、maackiain(MAE13)、β-谷甾醇(MAE15，β-sitoterol)、鸢尾种苷(MAE16，tectoridin)和afromosin 7-O-β-D-glucopyranoside(MAE17)。
其中化合物MAE5、7、10和11均为首次从该属植物中分离得到，化合物MAE8、12和13均为首次从该植物中分离得到。
Maackia amurensis Rupr. et Maxim., the plant of Leguminosae, has the antioxidant, antiradical, antitumour and anti-inflammation activities, being used to treat injuries from falls, bruise and gall, rheumatoid arthritis, ulcer and so on.
Seventeen compounds were separated from the EtOAc fraction of 70% ethanol extraction of M. amurensis by repeated silica gel column chromatography, Sephadex LH-20 column chromatography, recrystallization and so on.
Fourteen compounds' structures were identified on the basis of their physico-chemical properties and spectroscopic analysis. The compounds are shown as follows: tectorigenin(MAE2), genistein (MAE3), afromosin(MAE4), prunetin(MAE5), formononetin (MAE6), ononin 6"-O-acetate (MAE7), maackiaflavanone (MAE8), maackiain 3-O(6'-O-malonyl-β-D-glucopyranoside) (MAE10), maackiain 3-O-(6'-O-acetyl-β-D-glucopyranoside) (MAE11), di-O-methyldaidzein(MAE12), maackiain (MAE13), β-sitosterol (MAE15), tectoridin (MAE16) and afromosin 7-O-β-D-glucopyranoside (MAE17). Compounds MAE5, 7, 10 and 11 were isolated from this genus for the first time, and compounds MAE8, 12 and 13 were isolated from this species for the first time.
引文
[1] 刘娟，王良信．一种新的药用植物资源——怀槐[J]．中国野生植物资源，1997(1)：22-25．
[2] 曲香芝，李景道．朝鲜槐黄酮类成分的研究进展[J]．延边医学院学报，1993，16(3)：230-232．
[3] 韦直．中国植物志：40卷[M]．北京：科学出版社，1994，56-64．
[4] S. Ohmiya, H. Kubo, H. Otomasu, et al. Tashiromine; a new alkaloid from Maackia tashiroi [J]. Heterolycles, 1990, 30 (1): 537-542.
[5] O. B. Maksimov, O. E. Krivoshchekova, L. S. Stepanenko, et al. Isoflavones and stilbenes of the heartwood ofMaackia amurensis [J]. Chem Nat Compd, 1985 (6): 735-740.
[6] N. I. Kulesh, O. B. Maksimov, V. A. Denisenko , et al. Isoflavonoids from heartwood of Maackia amurensis Rupr. et Maxim [J]. Chem Nat Compd, 2001, 37 (1): 29-31.
[7] 黄文哲，段金廒，李正亮．怀槐的化学成分研究(Ⅱ)[J]．中国中药杂志，2001，26(6)：403-404．
[8] 黄文哲，段金廒，李正亮．怀槐的化学成分研究(Ⅰ)[J]．中国药科大学学报，2000，31(1)：8-10．
[9] A. N. Komissarenko, V. N. Kovalev, N. F. Komissarenko. Isoflavonoids of the bark and leaves of Maackia amurensis [J]. Chem Nat Compd, 1994, 30 (2): 264-265.
[10] 曲香芝，李景道，金光洙，等．朝鲜槐化学成分的研究[J]．中草药，1997，28(2)：72-73．
[11] M. Takai, H. Yamaguchi, T. Saitoh, et al. Chemical studies on the oriental plant drugs. ⅩⅩⅩⅤ. The chemical constituents of the heartwood of Maackia amurensis var. buergeri [J]. Chem Pharm Bull, 1972, 20 (11): 2488-2490.
[12] 曾佳烽，朱大元．光叶马鞍树根化学成分研究[J]．植物学报，1999，41(9)：997-1001．
[13] J. E Zeng, G. L. Li, X. Xu, et al. Two isoprenoid-substituted isoflavans from roots of Maackia tenuifolia [J]. Phytochemistry, 1996, 43 (4): 893-896.
[14] J. E Zeng, G. L. Li, J. K. Shen, et al. Manuifolins D, E, and F: new isoflavonoids from Maackia tenuifolia [J]. J Nat Prod, 1997, 60: 918-920.
[15] J. H. Shen, L. Wang, B. N. Zhou. Isolation, structure elucidation and synthesis of a new prenylated flavonol, maackiaflavonol, from Maackia tenuifolia [J]. Chinese Chemical Letters, 1991, 2 (8): 629-630.
[16] J. F.Zeng, H. X. Wei, G. L. Li, et al. Three prenylated isoflavans from Maackia tenuifolia [J]. Phytochemistry, 1998, 47 (5): 903-905.
[17] N. Matsuura, R. Nakai, M. linuma, et al. A prenylated flavanone from roots of Maackia amurensis subsp, buergeri [J]. Phytochemistry, 1994,, 36 (1): 255-256.
[18] Y. H. Wang, J. S. Li, Z. R. Jiang, et al. Lupin alkaloids from chinese Maackia arnurensis [J]. Chem Pharm Bull, 2000, 48 (5): 641-645.
[19] K. Saito, S. Tsai, S. Ohmiya, et aL (+)- 13β-Hydroxymamanine, a new lupin alkaloid from Maackia amurensis var. [J]. Chem Pharm Bull, 1986, 34 (9): 3982-3985.
[20] K. Saito, T. Yashino, T. Sekine, et al. Isolation of (+)-maackiamine (norammodendrine) from the flowers of Maackia amurensis [J]. Phytochemisty, 1989, 28 (9): 2533-2534.
[21] S. Ohmiya, H. Kubo, Y. Nakaaze, et al.(-)-Camoensidine N-Oxide; a new alkaloid from Maackia tashiroi [J]. Chem Pharm Bull, 1991, 39 (5): 1123-1125.
[22] Y. H. Wang, K. Higashiyama, H. Kubo, et al. A lupin alkaloid, (-)-tenuamine (norlusitanine) from maackia tenuifolia [J]. Heterocycles, 1999, 51 (12): 3001-3004.
[23] O. E. Krivoshchekova, L. S. Stepanenko, O. B. Maksimov. A new isoflavonostilbene from the heartwood of Maackia amurensis [J]. Chem Nat Compd, 1986 (1): 35-38.
[24] N. I. Kulesh, V. A. Denisenko, O. B. Maksimov. Stilbenolignan from Maackia amurensis [J]. Phytochemistry, 1995, 40 (3): 1001-1003.
[25] N. I. Kulesh, V. V. Isakov, O. B. Maksimov. Meric stilbenes of the wood of Maackia amurensis [J]. Chem Nat Compd, 1992 (5): 407-414.
[26] N. I. Kulesh, O. B. Maksimov, S. A. Fedoreev, et al. About native components of extracts from Maackia amurensis wood [J]. Chem Nat Compd, 1999, 35 (5): 575-579.
[27] 曲香芝，庄桂兰，金正男，等．朝鲜槐树皮的抗炎作用[J]．延边医学院学报，1996，19(1)：18-21．
[28] 黄文哲，赵小辰，王峥涛．异黄酮类化合物抗肿瘤细胞增殖作用[J]．现代中药研究与实践，2003，17(1)：50-51．
[29] 李应勤，陆蕴茹，魏璐雪．白射干黄酮类成分的研究[J]．药学学报，1986，21(11)：836-841．
[30] A. C. Talukdar, N. Jain, Shantanu De, et al. An isoflavone from Myristica malabarica [J]. Phytochemistry, 2000, 53: 155-157.
[31] B. Klejdus, D. V. Sterbova, V. Kuban. Identification of isoflavone conjugates in red clover by liquid chromatography-mass spectrometry after two-dimensional solid-phase extraction [J]. Analytica Chimica Acta, 2001, 450: 81-97.
[32] 海力茜，张庆英，梁鸿，等．多序岩黄芪化学成分研究[J]．药学学报，2003，38(8)：592-595．
[33] E. Bedir, I. Calis, R. Aquino, et al. Trojanoside H: a cycloartane-type glycoside from the aerial parts of Astragalus trojanus[J]. Phytochemistry, 1999, 51: 1017-1020.
[34] M. Komatsu, I. Yokoe, Y. Shirataki, et al. Trifolirhizin 6'-monoacetate, a new glycoside from the roots of Sophora subprostrata[J]. Phytochemistry, 1976, 15:1089-1090.
[35] H. Yamamoto, M. Ichimura, T. Tanaka, et al. A trifolirhizin malonate from Sophora flavescens var. Angustifolia and its stability[J]. Phytochemistry, 1991, 30 (5): 1732-1733.
[36] P. Stocker, M. Yousfi, C. Salmi, et al. Maackiain 3-O-(6'-O-malonyl-β-D-glucopyranoside) from Oudneya africana, a powerful inhibitor of porcine kidney acylase I[J]. Biochimie, 2005, 87:507-512.
[37] P. C. Stevenson, N. C. Veitch. Isoflavenes from the roots of Cicer Judaicum[J]. Phytochemistry, 1996, 43 (3): 695-700.
[2] 曲香芝，李景道．朝鲜槐黄酮类成分的研究进展[J]．延边医学院学报，1993，16(3)：230-232．
[3] 韦直．中国植物志：40卷[M]．北京：科学出版社，1994，56-64．
[4] S. Ohmiya, H. Kubo, H. Otomasu, et al. Tashiromine; a new alkaloid from Maackia tashiroi [J]. Heterolycles, 1990, 30 (1): 537-542.
[5] O. B. Maksimov, O. E. Krivoshchekova, L. S. Stepanenko, et al. Isoflavones and stilbenes of the heartwood ofMaackia amurensis [J]. Chem Nat Compd, 1985 (6): 735-740.
[6] N. I. Kulesh, O. B. Maksimov, V. A. Denisenko , et al. Isoflavonoids from heartwood of Maackia amurensis Rupr. et Maxim [J]. Chem Nat Compd, 2001, 37 (1): 29-31.
[7] 黄文哲，段金廒，李正亮．怀槐的化学成分研究(Ⅱ)[J]．中国中药杂志，2001，26(6)：403-404．
[8] 黄文哲，段金廒，李正亮．怀槐的化学成分研究(Ⅰ)[J]．中国药科大学学报，2000，31(1)：8-10．
[9] A. N. Komissarenko, V. N. Kovalev, N. F. Komissarenko. Isoflavonoids of the bark and leaves of Maackia amurensis [J]. Chem Nat Compd, 1994, 30 (2): 264-265.
[10] 曲香芝，李景道，金光洙，等．朝鲜槐化学成分的研究[J]．中草药，1997，28(2)：72-73．
[11] M. Takai, H. Yamaguchi, T. Saitoh, et al. Chemical studies on the oriental plant drugs. ⅩⅩⅩⅤ. The chemical constituents of the heartwood of Maackia amurensis var. buergeri [J]. Chem Pharm Bull, 1972, 20 (11): 2488-2490.
[12] 曾佳烽，朱大元．光叶马鞍树根化学成分研究[J]．植物学报，1999，41(9)：997-1001．
[13] J. E Zeng, G. L. Li, X. Xu, et al. Two isoprenoid-substituted isoflavans from roots of Maackia tenuifolia [J]. Phytochemistry, 1996, 43 (4): 893-896.
[14] J. E Zeng, G. L. Li, J. K. Shen, et al. Manuifolins D, E, and F: new isoflavonoids from Maackia tenuifolia [J]. J Nat Prod, 1997, 60: 918-920.
[15] J. H. Shen, L. Wang, B. N. Zhou. Isolation, structure elucidation and synthesis of a new prenylated flavonol, maackiaflavonol, from Maackia tenuifolia [J]. Chinese Chemical Letters, 1991, 2 (8): 629-630.
[16] J. F.Zeng, H. X. Wei, G. L. Li, et al. Three prenylated isoflavans from Maackia tenuifolia [J]. Phytochemistry, 1998, 47 (5): 903-905.
[17] N. Matsuura, R. Nakai, M. linuma, et al. A prenylated flavanone from roots of Maackia amurensis subsp, buergeri [J]. Phytochemistry, 1994,, 36 (1): 255-256.
[18] Y. H. Wang, J. S. Li, Z. R. Jiang, et al. Lupin alkaloids from chinese Maackia arnurensis [J]. Chem Pharm Bull, 2000, 48 (5): 641-645.
[19] K. Saito, S. Tsai, S. Ohmiya, et aL (+)- 13β-Hydroxymamanine, a new lupin alkaloid from Maackia amurensis var. [J]. Chem Pharm Bull, 1986, 34 (9): 3982-3985.
[20] K. Saito, T. Yashino, T. Sekine, et al. Isolation of (+)-maackiamine (norammodendrine) from the flowers of Maackia amurensis [J]. Phytochemisty, 1989, 28 (9): 2533-2534.
[21] S. Ohmiya, H. Kubo, Y. Nakaaze, et al.(-)-Camoensidine N-Oxide; a new alkaloid from Maackia tashiroi [J]. Chem Pharm Bull, 1991, 39 (5): 1123-1125.
[22] Y. H. Wang, K. Higashiyama, H. Kubo, et al. A lupin alkaloid, (-)-tenuamine (norlusitanine) from maackia tenuifolia [J]. Heterocycles, 1999, 51 (12): 3001-3004.
[23] O. E. Krivoshchekova, L. S. Stepanenko, O. B. Maksimov. A new isoflavonostilbene from the heartwood of Maackia amurensis [J]. Chem Nat Compd, 1986 (1): 35-38.
[24] N. I. Kulesh, V. A. Denisenko, O. B. Maksimov. Stilbenolignan from Maackia amurensis [J]. Phytochemistry, 1995, 40 (3): 1001-1003.
[25] N. I. Kulesh, V. V. Isakov, O. B. Maksimov. Meric stilbenes of the wood of Maackia amurensis [J]. Chem Nat Compd, 1992 (5): 407-414.
[26] N. I. Kulesh, O. B. Maksimov, S. A. Fedoreev, et al. About native components of extracts from Maackia amurensis wood [J]. Chem Nat Compd, 1999, 35 (5): 575-579.
[27] 曲香芝，庄桂兰，金正男，等．朝鲜槐树皮的抗炎作用[J]．延边医学院学报，1996，19(1)：18-21．
[28] 黄文哲，赵小辰，王峥涛．异黄酮类化合物抗肿瘤细胞增殖作用[J]．现代中药研究与实践，2003，17(1)：50-51．
[29] 李应勤，陆蕴茹，魏璐雪．白射干黄酮类成分的研究[J]．药学学报，1986，21(11)：836-841．
[30] A. C. Talukdar, N. Jain, Shantanu De, et al. An isoflavone from Myristica malabarica [J]. Phytochemistry, 2000, 53: 155-157.
[31] B. Klejdus, D. V. Sterbova, V. Kuban. Identification of isoflavone conjugates in red clover by liquid chromatography-mass spectrometry after two-dimensional solid-phase extraction [J]. Analytica Chimica Acta, 2001, 450: 81-97.
[32] 海力茜，张庆英，梁鸿，等．多序岩黄芪化学成分研究[J]．药学学报，2003，38(8)：592-595．
[33] E. Bedir, I. Calis, R. Aquino, et al. Trojanoside H: a cycloartane-type glycoside from the aerial parts of Astragalus trojanus[J]. Phytochemistry, 1999, 51: 1017-1020.
[34] M. Komatsu, I. Yokoe, Y. Shirataki, et al. Trifolirhizin 6'-monoacetate, a new glycoside from the roots of Sophora subprostrata[J]. Phytochemistry, 1976, 15:1089-1090.
[35] H. Yamamoto, M. Ichimura, T. Tanaka, et al. A trifolirhizin malonate from Sophora flavescens var. Angustifolia and its stability[J]. Phytochemistry, 1991, 30 (5): 1732-1733.
[36] P. Stocker, M. Yousfi, C. Salmi, et al. Maackiain 3-O-(6'-O-malonyl-β-D-glucopyranoside) from Oudneya africana, a powerful inhibitor of porcine kidney acylase I[J]. Biochimie, 2005, 87:507-512.
[37] P. C. Stevenson, N. C. Veitch. Isoflavenes from the roots of Cicer Judaicum[J]. Phytochemistry, 1996, 43 (3): 695-700.