中藥材石斛、益母草、辛夷化學成分研究

Phytochemical Studies on the Chinese Medicine of Ephemerantha lonchophylla, Dendrobium antennatum, Leonurus japonicas and Magnolia biondii

張金鳴(Jin-Ming Chang)

指導教授 ： 陳建志 ； 謝博進

中原大學/理學院/化學研究所/博士(2010年)

https://doi.org/10.6840/cycu201000774

摘要

摘 要
本研究針對中藥材石斛（包括有瓜石斛Ephemerantha lonchophyll 和羚羊石斛Dendr-obium antennatum Lindl.）、益母草Leonurus japonicus和辛夷 Magnolia biondii進行化學成分的分離純化和結構鑑定。其中自有瓜石斛中分離純化得到8個化合物，分別為2- hydroxy-3,4,7-trimethoxyphenanthrene (1), 8-hydroxy-2,3,4,7-tetramethoxy-9,10-dihydro- phenanthrene (2), denbinobin (3), 2,3,4,7-tetramethoxy-9,10-dihydrophenanthrene (4), 2,5-dihydroxy-3,4-dimethoxyphenanthrene (5), 3-hydroxy-2,4,7-trimethoxyphenanthrene (6), 3-hydroxy-2,4,7-trimethoxy-9,10-dihydrophenanthrene (7) 和 2,8-dihydroxy-3,4,7-tri-methoxy-9,10-dihydrophenanthrene (8)。其中化合物1和2為首次發現的新化合物；自羚羊石斛地上部的酒精萃取物水可溶部份分離純化得到13個化合物，鑑定其結構分別為： 4-hydroxy-3-methoxybenzaldehyde (9), 3,4,5-trimethoxybenzoic acid (10), p-hydroxybenzaldehyde (11), nudol (2,7-dihydroxy-3,4-dimethoxyphenanthrene) (12), moscatin (13), gigantol (3’,4-dihydroxy-5,5’-dimethoxydihydrostilbene ) (14), benzoic acid (15), (+)-sy-ri-ngaresinol (16), (+)-pinoresinol (17), quercetin (18), N-(tran-p-coumaroyl)tyramine (19), 3,4-dihydroxybenzoic acid (20), and (2-hydroxyphenyl)-β-D-glucopyranoside (21)，化合物 16 和 17 是屬木質素類，雖存在於多種植物中，但被發現於石斛屬植物中，尚屬首次，化合物21為首次由天然界分離得到；自益母草中分離純化得到9個化合物， 1,6-di-O-syringoyl--D-glucose (22) and quercetin 3-O-[(3-O-syringoyl--L-rhamnopyra-nosyl)-(16)--D-glucopyranoside] (23) 6-hydroxy-15,16-epoxylabda-5,8,13(16),14-tetra-en-7- one (24), 6-hydroxy-15,16-epoxylabda-8,13(16),14-trien-7-one (25), genkwa-nin (26), apigenin (27), quercetin (28), tiliroside (29), and uracil (30)，其中化合物22和23為首次發現的新化合物；自辛夷中分離得到8個化合物，分別為tiliroside (31), pinoresinol- dimethyl ether (32), magnolin (33), lirioresinol-B dimethyl ether (34), epi-magnolin A (35), fargesin (36) demethoxyaschantin (37)及 epi-fargesin (38)，並建立一高效液相層析分析方法，可同時測定辛夷及其製劑中上述8個指標成分之含量，針對台灣市售的 10 種辛夷原料及7種辛夷製劑中 8 個指標成分含量進行了分析檢測，結果顯示該分析方法標準曲線之線性關係、精密度、準確度和穩定性具佳，可作為中藥辛夷原料和製劑的品管方法。

關鍵字

有瓜石斛 ； 羚羊石斛 ； 益母草 ； 辛夷

並列摘要

Abstract
In our research of chemical constituents of Ephemerantha lonchophylla, Dendrobium antennatum Lindl, Leonurus japonicus and Magnolia biondii, thirty eight compounds were isolated, their structures were characterized by spectroscopic and chemical methods.
Six known compounds, denbinobin (3), 2,3,4,7-tetramethoxy-9,10-dihydro- phenanthrene (4) , 2,5-dihydroxy-3,4-dimethoxyphenanthrene (5) , 3-hydroxy-2,4,7-trimethoxyphenanthrene (6), 3-hydroxy-2,4,7-trimethoxy-9,10-dihydrophenanthrene (7), and 2,8-dihydroxy-3,4,7-trimethoxy-9,10-dihydrophenanthrene (8) , and two new compounds, 2-hydroxy-3,4,7-trimethoxyphenanthrene (1), 8-hydroxy-2,3,4,7-tetramethoxy-9,10-dihydrophenanthrene (2), were isolated from the aerial parts of Ephemerantha lonchophylla; Thirteen components, 4-hydroxy-3-methoxybenzaldehyde (9), 3,4,5-trimethoxybenzoic acid (10), p-hydroxybenzaldehyde (11), nudol (2,7-dihydroxy-3,4-dimethoxyphenanthrene) (12), moscatin (13), gigantol (3’,4-dihydroxy-5,5’-dimethoxydihydrostilbene ) (14), benzoic acid (15), (+)-syringaresinol (16), (+)-pinoresinol (17), quercetin (18), N-(tran-p-coumaroyl)tyramine (19), 3,4-dihydroxybenzoic acid (20), and (2-hydroxyphenyl)-β-D-glucopyranoside (21), were isolated from the water-soluble part of EtOH extract of the dried aerial parts of Dendrobium antennatum Lindl., Compound 21 was isolated for the first time from a natural source, although it was synthesized in laboratory. Compounds 16 and 17 are lignans and exist in a lot of plants, however, it is the first time for them to be found in the Dendrobium species; From the aerial parts of Leonurus japonicas, two new phenolic glycosides 1,6-di-O-syringoyl--D-glucose (22) and quercetin 3-O-[(3-O-syringoyl--L-rhamnopyranosyl)-(16)--D-glucopyranoside] (23) , were isolated together with seven- known compounds, 6-hydroxy-15,16-epoxylabda-5,8,13(16),14-tetraen-7-one (24), 6-hydroxy-15,16-epoxylabda-8,13(16),14-trien-7-one (25), genkwanin (26), apigenin (27), quercetin (28), tiliroside (29), and uracil (30). Furthermore, a reversed-phase liquid chromatographic method was developed for the quantitative determination of eight components, tiliroside (31), pinoresinol dimethyl ether (32), magnolin (33), lirioresinol-B dimethylether (34), epi-magnolin A (35), fargesin (36) , demethoxyaschantin (37) and epi-fargesin (38) in Flos Magnoliae and its concentrated products. The current assay method was applied to quantitative determination of 10 different samples of Flos Magnoliae and its 7 concentrated products. The results indicated that the developed method could be readily utilized as a quality control method for Flos Magnoliae and its concentrated products.

並列關鍵字

Magnolia biondii ； Ephemerantha lonchophylla ； Leonurus japonicus ； Dendrobium antennatum Lindl

參考文獻

26 Lin TH, Chang SJ, Chen CC, Constituents from the Stems of Dendrobium moniliforme, Chin. Pharm. J. 52: 251-259, 2000.

31 Huang YL, Lay HL, Shen CC, Chen FC, Chen CC. Stilbenoids from the Stems of Dendrobium sonia. Chin. Pharm. J. 52: 305-311, 2000.

34 Chen CC, Huang HY, Shen CC, Huang YL, Ou JC. Chemical Constituents of Verbena bonariensis. Chin. Pharm. J. 55: 65-70, 2003.

2 Chen, H.Y., Shiao, M.S., Huang, Y.L., Shen, C.C., Lin, Y.L., Kuo, Y.H., Chen, C.C., An tioxidant principles from Ephemerantha lonchophyla J. Nat. Prod. 62: 1225-1227,1999.

3 Chen, C.C., Huang, Y.L., Teng, C.M., Antiplatelet aggregation principles from Ephemerantha lonchophyla Planta Med. 66: 372-374, 2000.