食茱萸枝條及玉蘭枝條之化學成分及生物活性之研究

Studies on the Chemical Constituents and Biological Activities from the Twigs of Zanthoxylum ailanthoides and Twigs of Magnolia denudata

鍾靜宜(Ching-Yi Chung)

指導教授 ： 鍾美英

高雄醫學大學/藥學院/藥學系博士班/博士(2018年)

摘要

食茱萸(Zanthoxylum ailanthoides)為芸香科(Rutaceae)之帶刺落葉喬木，分佈於中國、日本、韓國、菲律賓及台灣。玉蘭(Magnolia denudata)為木蘭科(Magnoliaceae)之落葉性喬木，分佈於中國東南部。
　　由食茱萸枝條之EtOAc可溶部，分離出一個新的benzo[c]phenanthridine：oxynorchlerythrine (1), 二個新的benzenoid derivatives: methyl 4-(2-hydroxy-4-methoxy-3-methyl-4-oxobutoxy)- benzoate (2)及(E)-methyl 4-(4-((Z)-3-methoxy-3-oxoprop-1-enyl)- phenoxy)-2-methylbut-2-enoate (3)，以及11個已知化合物(4~14)。11個已知化合物分別包括二個benzo[c]phenanthridines：decarine (4)和6-acetonyldihydrochelerythrine (5)，五個 lignans：(–)-syringaresinol (6), 5′,5′′-didemethoxypinoresinol (7), (+)-episesamin (8), glaberide I (9)及 (–)-dihydrocubebin (10)，一個 coumarin：xanthyletin (11)，一個 lactone：lanyulactone (12)以及兩個 benzenoids：methyl 3,4-dimethoxybenzoate (13)及p-hydroxybenzoic acid (14)。
由玉蘭枝條之EtOAc可溶部，目前已分離出兩個新化合物，biphenyl-type neolignan derivatives：2-[2-(hydroxymethyl)-1-benzofuran- 5-yl]-4-(prop-2-en-1-yl)phenol (15) 及2′-ethoxy-5,5′-di(prop-2-en-1-yl)- biphenyl-2-ol (16)，及6個已知化合物(17~22)。6個已知化合物分別包括兩個lignans, fargesin (17)及rel-(7R,8S,8S′)-3,4,3′,4′-tetramethoxy-9,7′- dihydroxy-8.8′,7.O.9′-lignan (18)，一個stilbene derivative：resveratrol (19)，兩個biphenyl-type neolignans, magnolol (20)及honokiol (21)及一個benzenoid：vanillic acid (22)。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。
目前分離得到的化合物中，decarine (4), (–)-syringaresinol (6), (+)-episesamin (8), glaberide I (9), (–)-dihydrocubebin (10), xanthyletin (11), magnolol (20)及honokiol (21)對於N-formyl-L-methionyl-L-leucyl-L- phenylalanine/cytochalasin B (fMLP/CB)所誘導人類嗜中性白血球產生超氧陰離子，具有良好的抑制活性 (IC50值 ≤ 4.79 g/mL)。
此外，化合物decarine (4), (+)-episesamin (8),xanthyletin (11), 2-[2-(hydroxymethyl)-1-benzofuran-5-yl]-4-(prop-2-en-1-yl)phenol (15), 2′-ethoxy-5,5′-di(prop-2-en-1-yl)biphenyl-2-ol (16), magnolol (20)及vanillic acid (22)對於fMLP/CB所誘導彈性蛋白酶的釋放，亦具有良好的抑制活性 (IC50值 ≤ 6.40 g/mL)。

關鍵字

食茱萸 ； 玉蘭 ； 枝條 ； 生物活性

並列摘要

Zanthoxylum ailanthoides Sieb. & Zucc. (Rutaceae) is a medium-to large-sized tree found at low altitude in forests of China, Japan, Korea, the Philippines, and Taiwan. Magnolia denudata (Magnoliaceae) is a deciduous tree, natively distributed in southeastern China.
In our search for compounds with anti-inflammatory activities, a new benzo[c]phenanthridine, oxynorchlerythrine (1), and two new benzenoid derivatives, methyl 4-(2-hydroxy-4-methoxy-3-methyl-4-oxobutoxy)- benzoate (2) and (E)-methyl 4-(4-((Z)-3-methoxy-3-oxoprop-1-enyl)- phenoxy)-2-methylbut-2-enoate (3), and 11 known compounds (4–14) have been isolated and identified from the EtOAc-soluble fraction the twigs of Z. ailanthoides. Eleven known compounds include two benzo[c]phenan- thridines, decarine (4) and 6-acetonyldihydrochelerythrine (5), five lignan derivatives, (–)-syringaresinol (6), 5′,5′′-didemethoxypinoresinol (7), (+)-episesamin (8), glaberide I (9), and (–)-dihydrocubebin (10), a coumarin, xanthyletin (11), a lactone, lanyulactone (12), and two benzenoids, methyl 3,4-dimethoxybenzoate (13) and p-hydroxybenzoic acid (14).
Investigation on the EtOAc-soluble fraction of the twigs of M. denudata led to the isolation of two new biphenyl-type neolignan derivatives, 2-[2-(hydroxymethyl)-1-benzofuran-5-yl]-4-(prop-2-en-1-yl)- phenol (15) and 2′-ethoxy-5,5′-di(prop-2-en-1-yl)biphenyl-2-ol (16), and 6 known compounds (17–22). Six known compounds include two lignans, fargesin (17) and rel-(7R,8S,8S′)-3,4,3′,4′-tetramethoxy-9,7′-dihydroxy- 8.8′,7.O.9′-lignan (18), a stilbene derivative, resveratrol (19), two biphenyl-type neolignans, magnolol (20) and honokiol (21), and a benzenoid, vanillic acid (22). The structures of all isolates were determined through spectral analyses and comparison of their physical and spectral data with literatures.
Among the isolated compounds, decarine (4), (–)-syringaresinol (6), (+)-episesamin (8), glaberide I (9), (–)-dihydrocubebin (10), xanthyletin (11), magnolol (20), and honokiol (21) exhibited potent inhibition (IC50 values ≤ 4.79 g/mL) of superoxide anion generation by human neutrophils in response to formyl-L-methionyl-L-leuckyl-L-phenylalanine/ cytochalasin B (fMLP/CB).
In addition, decarine (4), (+)-episesamin (8), xanthyletin (11), 2-[2-(hydroxymethyl)-1-benzofuran-5-yl]-4-(prop-2-en-1-yl)phenol (15), 2′-ethoxy-5,5′-di(prop-2-en-1-yl)biphenyl-2-ol (16), magnolol (20), and vanillic acid (22) also inhibited fMLP/CB-induced elastase release with IC50 values ≤ 6.40 g/mL.

並列關鍵字

Zanthoxylum ailanthoides ； Magnolia denudata ； Twigs ； Biological Activities

參考文獻

1. Chang, C. E.; Hartley, T. G. Rutaceae in Flora of Taiwan, 2nd edition. Editorial Committee of the Flora of Taiwan, Taipei: 1993, Vol 3: pp 510-544.

2. 歐辰雄、何東輯.自然保育季刊-『台灣產芸香科植物介紹 (IX)-花椒屬2』，行政院農委會特有生物研究保育中心，南投，1997,第十七期，pp 17-23。

3. 新編中藥大辭典，新文豐出版公司，台北，1982, pp 1412-1413。

4. Gan, W. S. Manual of Medicinal Plants in Taiwan; National Research Institute of Chinese Medicine: Taiwan, 1970, 2, p 375.

5. 劉棠瑞，台灣木本植物圖誌，國立台灣大學農學院，台北，1962, p 884。