細葉紫珠枝葉之萜類成分研究

Studies on the terpenoids from the twigs and leaves of Callicarpa pilosissima

劉苑瑋(Yuan-Wei Liu)

指導教授 ： 沈雅敬

國立臺灣大學/醫學院/藥學研究所/碩士(2011年)

https://doi.org/10.6342/NTU.2011.01711

摘要

本論文主要在研究細葉紫珠 (Callicarpa pilosissima) 含有之萜類化合物，將其枝葉部份用酒精萃取，使用各種的管柱色層分析方法進行分離鑑定所含之化學組成成份。實驗結果共分離了九個化合物，其中包括了四個新的萜類化合物。

分離得到的化合物中，共有三個屬於 3,4-seco-abietane 骨架的雙萜類新化合物 Callipilosins A~C (1~3)、一個 labdenoic-type 的雙萜類新化合物 Callipilosin D (4)、以及五個已知化合物 ursolic acid (5)、3-oxoanticopalic acid (6)、(E)-6β- hydroxylabda-8(17),13-dien-15-oic acid (7)、5-hydroxy-3,6,7,4'- tetramethoxyflavone (8)、artemetin (9)。

以上化合物的結構是利用核磁共振圖譜 1D NMR (1H-NMR、13C-NMR) 及 2D NMR (COSY、HMQC、HMBC、NOESY) 加上各種物理數據分析，包括旋光度、紅外線、紫外線、CD 光譜及高解析電灑式質譜儀，並參考相關文獻而確認。另外化合物1為結晶物質，其結構與相對立體結構更經由 X-ray 單晶繞射解析做更進一步的證明。此外，化合物4利用與文獻比對旋光數值定立其絕對立體結構。

最後將所分得的化合物進行抗癌、抗發炎等生物活性檢測。

關鍵字

細葉紫珠 ； 3,4-seco-abietane ； labdenoic-type ； 雙萜類 ； flavone

並列摘要

This research is a chemical investigation of the terpenoid constituents from Callicarpa pilosissima. The ethanol extracts of the twigs and leaves of C. pilosissima were separated by extensive column chromatography to give nine compounds, including four new terpenoids.

Callipilosins A~C (1~3) belong to new diterpenes of 3,4-seco-abietane-type while callipilosin D is a new analog of labdenoic-type diterpene. In addition, five known compounds were isolated including a triterpene, ursolic acid (5), two labdenoic-type diterpenes, 3-oxoanticopalic acid (6) and (E)-6β-hydroxylabda- 8(17),13-dien-15-oic acid (7), and two flavons, 5-hydroxy-3,6,7,4'-tetramethoxy- flavone (8) and artemetin (9).

The structures of these compounds were determined on the basis of spectroscopic analyses, such as 1D-NMR (1H and 13C-NMR) and 2D-NMR (COSY, HMQC, HMBC, NOESY) techniques, physical methods including optical rotation, IR, UV, CD, HRESIMS, as well as by comparison with the published data. Moreover, compound 1 was further confirmed by X-ray crystallographic analysis. The absolute stereochemistry of compound 4 was determined by optical rotation data.

All the isolated components were tested biological activities including anti-tumor and anti-inflammatory effects.

並列關鍵字

Callicarpa pilosissima ； 3,4-seco-abietane ； labdenoic-type ； diterpene ； flavone

參考文獻

2. Jones, W.P.; A.D. Kinghorn. “Biologically Active Natural Products of The Genus Callicarpa.” Curr. Bioact. Compd. 2008, 4(1), 15-32.

5. Van den Berghe, D.A.; Ieven, M.; Mertens, F.; Vlietinck, A.J.; Lammens, E. “Screening of higher plants for biological activities. II Antiviral activity.” Lloydia 1978, 41, 463-471.

6. Tingle, F.C.; Mitchell, E.R. “Aqueous extracts from indigenous plants as oviposition deterrents forHeliothis virescens (F.).” J. Chem. Ecol. 1984, 10, 101-113.

7. Tellez, M.R.; Dayan, F.E.; Schrader, K.K.; Wedge, D.E.; Duke, S.O. “Composition and some biologicalactivities of the essential oil of Callicarpa americana (L.).” J. Agric Food Chem. 2000, 48, 3008-3012.

8. Cantrell, C. L.; Klun, J. A.; Bryson, C. T.; Kobaisy, M.; Duke, S. O. “Isolation and Identification of Mosquito Bite Deterrent Terpenoids from Leaves of American (Callicarpa americana) and Japanese (Callicarpa japonica) Beautyberry.” J. Agric. Food Chem. 2005, 53, 5948-5953.