白木香樹脂材部、蘭嶼肉豆蔻果實、蘭嶼肉桂花部及山芙蓉莖部之化學成分及生物活性之研究

Studies on the Chemical Constituents and Biological Activities from the Resinous Wood of Aquilaria sinensis, the Fruits of Myristica cagayanensis, the Flowers of Cinnamomum kotoense and the Stems of Hibiscus taiwanensis

王馨翎(Sin-Ling Wang)

指導教授 ： 鍾美英

共同指導教授 ： 陳日榮(Jih-Jung Chen)

高雄醫學大學/藥學院/藥學系博士班/博士(2020年)

摘要

白木香[Aquilaria sinensis (Lour.) Spreng.]為瑞香科(Thymelaeaceae)之常綠喬木，為中國特有種植物，分布於廣東、廣西、海南等地。蘭嶼肉豆蔻[Myristica cagayanensis Merr]為肉豆蔻科(Myristicaceae)之常綠中型喬木，分佈於於菲律賓、台灣蘭嶼及綠島。蘭嶼肉桂[Cinnamomum kotoense Kanehira et Sasaki]為樟科(Lauraceae)台灣特有種之常綠喬木，分佈於台灣蘭嶼。而山芙蓉[Hibiscus taiwanensis Hu]為錦葵科(Malvaceae)台灣特有種之灌木，分布於台灣中低海拔地區。對台灣產植物進行抗發炎活性篩選，其中白木香、蘭嶼肉豆蔻、蘭嶼肉桂及山芙蓉皆為活性植物。
由白木香樹脂材部之EtOAc可溶部，目前已分離出十個新的2-(2-phenylethyl)chromenone衍生物:5-hydroxy-6-methoxy-2-[2-(3′-meth-oxyphenyl)ethyl]chromone (1)、5-hydroxy-6-methoxy-2-[2-(3′-hydroxy-phenyl)ethyl]chromone (2)、5,6-dihydroxy-2-[2-(4′-methoxyphenyl)-ethyl]chromone (3)、5,6-dihydroxy-2-[2-(3′-hydroxy-4′-methoxyphenyl)-ethyl]chromone (4)、6-hydroxy-5-methoxy-2-(2-phenylethyl)chromone (5)、6-hydroxy-5-methoxy-2-[2-(4′-methoxyphenyl)ethyl]chromone (6), 6,7-dimethoxy-2-[2-(2′-methoxyphenyl)ethyl]chromone (7)、7-methoxy-2-[2-(4′-methoxyphenyl)ethyl]chromone (8)、7-hydroxy-2-[2-(4′-meth-oxyphenyl)ethyl]chromone (9)及7-chloro-8-hydroxy-2-[2-(4′-methoxy-phenyl)ethyl]chromone (10)和一個chromone derivative: 6,7-dimethoxy-2-(2-methoxycarbonylethyl)chromone (11)，以及三十二個已知化合物(12~43)；由蘭嶼肉豆蔻果實之EtOAc可溶部，目前已分離出五個新的diarylnonanoids: myriscagayanone A–E (44~48)，四個新的dimeric diarylnonanoids: myriscagayanone F–I (49~52)和一個新的isoflavone: 4′,7-dihydroxy-2′,8-dimethoxyisoflavone (53)，以及二十八個已知化合物(42、54~80)；由蘭嶼肉桂花部之EtOAc可溶部，目前已分離出六個已知化合物(81~86)；另外自山芙蓉莖部之EtOAc可溶部，分離出二十三個已知化合物(42、86、87~107)。上述化合物之結構，經由各種圖譜分析及文獻數據比對予以確認。
目前分離所得到的化合物中，5,6-dihydroxy-2-[2-(4′-methoxyphenyl)ethyl]chromone (3)、(E)-1-(2′-hydroxyphenyl)-5-phenyl-pent-1-ene-3-one (12)、5,6-dihydroxy-2-(2-phenylethyl)chromone (14)、5,8-dihydroxy-2-(2-phenylethyl)chromone (21)、12,15-dioxo-α-selinen-4,11-dien (35)、myriscagayanone C (46)、genistein (58)、(−)-hinokinin (61)、(−)-haplomyrfolin (62)、demethyldactyyloidin (76)、isootusilactone A (81)及trans-ferulic acid (91)對於formyl-L-methionyl-L-leuckyl-L-phenylalanine (fMLP)誘導人類嗜中性白血球產生超氧陰離子(O2•–)，具有良好的抑制活性 (IC50 ≤ 6.45 M)。

關鍵字

白木香 ； 蘭嶼肉豆蔻 ； 蘭嶼肉桂 ； 山芙蓉 ； 抗發炎活性

並列摘要

Aquilaria sinensis (Lour.) Spreng. (Thymelaeaceae) is an evergreen tree species endemic to China and distributed in Guangdong, Guangxi, Hainan. Myristica cagayanensis Merr (Myristicaceae) is a medium-sized evergreen tree distributed in Philippines and Lanyu of Taiwan. Cinnamomum kotoense Kanehira et Sasaki (Lauraceae) is an evergreen tree and indigenous to Lanyu of Taiwan. Hibiscus taiwanensis Hu (Malvaceae) is an endemic shrub distributed in low to middle elevation regions throughout Taiwan. In our studies on the anti-inflammatory constituents of Formosan plants, many species have been screened for in vitro anti-inflammatory activity. Among them, A. sinensis, M. cagayanensis, C. kotoense and H. taiwanensis have been found to be the active species.
Ten new 2-(2-phenylethyl)chromenone derivatives: 5-hydroxy-6-methoxy-2-[2-(3′-methoxyphenyl)ethyl]chromone (1), 5-hydroxy-6-methoxy-2-[2-(3′-hydroxyphenyl)ethyl]chromone (2), 5,6-dihydroxy-2-[2-(4′-methoxy-phenyl)ethyl]chromone (3), 5,6-dihydroxy-2-[2-(3′-hydroxy-4′-methoxyphenyl)ethyl]chromone (4), 6-hydroxy-5-methoxy-2-(2-phenylethyl)chromone (5), 6-hydroxy-5-methoxy-2-[2-(4′-methoxy-phenyl)ethyl]chromone (6), 6,7-dimethoxy-2-[2-(2′-methoxyphenyl)-ethyl]chromone (7), 7-methoxy-2-[2-(4′-methoxyphenyl)ethyl]chromone (8), 7-hydroxy-2-[2-(4′-methoxyphenyl)ethyl]chromone (9), 7-chloro-8-hydroxy-2-[2-(4′-methoxyphenyl)ethyl]chromone (10), and a chromone derivative: 6,7-dimethoxy-2-(2-methoxycarbonylethyl)chromone (11), and 32 known compounds (12~43) have been isolated and identified from the resinous wood of A. sinensis. Investigation of EtOAc-soluble fractions of the fruits of M. cagayanensis led to the isolation of five new diarylnonanoids, myriscagayanones A–E (44~48), four new dimeric diarylnonanoids, myriscagayanones F–I (49~52), and a new isoflavone, 4′,7-dihydroxy-2′,8-dimethoxyisoflavone (53), along with 28 known compounds (42, 54~80). An EtOAc-soluble fractions of the flowers from C. kotoense, we have isolated 6 known compounds (81~86). In addition, investigation of EtOAc-soluble fractions of the stems of H. taiwanensis has led to the isolation of 23 known compounds (42, 86, 87~107). The structures of all isolates were determined through spectral analyses and comparison of their physical and spectral data with literatures.
Among the isolated compounds, 5,6-dihydroxy-2-[2-(4′-methoxy-phenyl)ethyl]chromone (3), (E)-1-(2′-hydroxyphenyl)-5-phenylpent-1-ene-3-one (12), 5,6-dihydroxy-2-(2-phenylethyl)chromone (14), 5,8-dihydroxy-2-(2-phenylethyl)chromone (14), 12,15-dioxo-α-selinen-4,11-dien (35), myriscagayanone C (46), genistein (58), (−)-hinokinin (61), (−)-haplomyrfolin (62), demethyldactyyloidin (76), isootusilactone A (81), and trans-ferulic acid (91) exhibited potent inhibition (IC50 values ≤ 6.45 M) on superoxide anion generation by human neutrophils in response to formyl-L-methionyl-L-leuckyl-L-phenylalanine (fMLP).

並列關鍵字

Aquilaria sinensis (Lour.) Spreng. ； Myristica cagayanensis Merr ； innamomum kotoense Kanehira et Sasaki ； Hibiscus taiwanensis Hu ； Anti-inflammatory activities

參考文獻

1. Wang, Y. Z.; Michael, G. G.; Brian, M.; Christopher, D. B.; Lorin, I. N. Thymelaeaceae in Flora of China, Science Press: Beijing, China & Missouri Botanical Garden Press: St. Louis, USA, 2007; Vol. 13 , pp 213-250.

2. Liao, J. C. Myristicaceae in Flora of Taiwan, 2nd ed., Editorial Committee of the Flora of Taiwan: Taipei, Taiwan, 1993; Vol. 2, pp 420-422.

3. Liao, J. C. Lauraceae in Flora of Taiwan, 2nd ed., Editorial Committee of the Flora of Taiwan: Taipei, Taiwan, 1993; Vol. 2, pp 433-499.

4. Chang, C. E. Malvaceae in Flora of Taiwan, 2nd ed., Editorial Committee of the Flora of Taiwan: Taipei, Taiwan, 1993; Vol. 3, pp 737-753.

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