華中五味子果實與紅果椌木枝葉之活性成分研究

Abstract

本論文分為兩個部分，第一部分為研究華中五味子(Schisandra sphenathera)之萜類與木質酚素活性成分，第二部分為研究紅果椌木(Dysoxylum hongkongense)之萜類與固醇類活性成分。 華中五味子果實部位之乙醇萃取物，利用各式管柱色層分析方法分離化合物，實驗結果共分離出24個化合物，包括8個新的化合物，其中1個屬於木質酚素類化合物Schiscupatetralin (A1)，7個屬於倍半萜類化合物(-)-Cuparenic methyl ester (A2)、(-)-Cuparenol methyl ether (A3)、(-)-15-Methoxy-3,6-peroxo-cupar-1-ene (A4, A5)、(+)-γ-Norcuparenol (A6)、Schisansphenin C (A7)、Schisansphenin D (A8)；以及16個已知化合物Methylgomisin O (A9)、Arisantetralone A (A10)、Arisantetralone C (A11)、Gomisin C (A12)、Methylgomisin R (A13)、Gomisin S (A14)、Interiotherin A (A15)、Macelignan (A16)、Deoxyschizandrin (A17)、Campherenol (A18)、Chamigrenal (A19)、γ-Cuparenal (A20)、Cuparenic acid (A21)、δ-Cuparenol (A22)、p-Hydroxybenzoic acid (A23)、Kadsuric acid (A24)。 紅果椌木枝葉部位之乙醇萃取物，利用各式管柱色層分析方法分離化合物，實驗結果共分離出18個化合物，包括14個屬於雙萜類之新化合物B1-B14，分別命名為Dysongensins A-N，1個首次於天然物中分離獲得之化合物cis-5α-Pregn-17(20)-en-3,16-dion (B15)，以及3個已知化合物3-Keto sclareolide (B16)、2β,3β,4β-Trihydroxypregnan-16-one (B17)、Isoscopoletin (B18)。 以上分離獲得之化合物利用核磁共振圖譜1D NMR (1H-NMR、13C-NMR)及2D NMR (HMQC、HMBC、COSY、NOESY)，並加上各種物理數據；如比旋光度、紅外線光譜、紫外線光譜、圓二色性光譜、高解析電灑式質譜，並利用化學資料庫Reaxys與SciFinder查詢相關文獻以鑑定結構。最後將所獲得之化合物進行抗病毒、抗發炎與抗癌等生物活性檢測。

This thesis is divided into two parts. The first part is the phytochemical investigation of terpenoids and lignans from Schisandra sphenanthera. The second part is the exploration of terpenoids and steroids from Dysoxylum hongkongense. Fractionation of the ethanol extract from the fruits of Schisandra sphenanthera has resulted in the isolation of twenty four compounds by extensive chromatography. Among them, schiscupatetralin A (A1), (-)-cuparenic methyl ester (A2), (-)-cuparenol methyl ether (A3), (-)-15-methoxy-3,6-peroxo-cupar-1-ene (A4, A5), (+)-γ-norcuparenol (A6), schisansphenin C (A7) and schisansphenin D (A8) are new compounds. In addition, sixteen known compounds were also isolated and characterized as methylgomisin O (A9), arisantetralone A (A10), arisantetralone C (A11), gomisin C (A12), methylgomisin R (A13), gomisin S (A14), interiotherin A (A15), macelignan (A16), deoxyschizandrin (A17), campherenol (A18), chamigrenal (A19), γ-cuparenal (A20), cuparenic acid (A21), δ-cuparenol (A22), p-hydroxybenzoic acid (A23) and kadsuric acid (A24). Investigation of the ethanol extract from the twigs and leaves of Dysoxylum hongkongense led to the isolation of eighteen compounds by using chromatographic methods. Among them, compounds B1-B14 are new diterpenoids designated dysongensins A-N. Compound B15 named cis-5α-pregn-17(20)-en-3,16-dion was obtained from natural source for the first time. Three known compounds, 2β,3β,4β-trihydroxypregnan-16-one (B16), 3-keto sclareolide (B17) and isoscopoletin (B18) were also isolated. The above structures were elucidated on the basis of spectroscopic analysis such as 1D-NMR (1H-NMR、13C-NMR), 2D NMR (HMQC、HMBC、COSY、NOESY) techniques and physical methods including optical rotation, infrared spectroscopy (IR), ultraviolet spectroscopy (UV), circular dichroism spectroscopy (CD) and high resolution mass spectroscopy (HRMS). Besides, the data of all compounds were compared with the published literatures by searching the chemical database of REAXYS and SciFinder. Finally, these compounds were tested and evaluated their biological activities including anti-virus, anti-inflammatory and anti-tumor effects.