論文使用權限 Thesis access permission:校內外都一年後公開 withheld
開放時間 Available:
校內 Campus: 已公開 available
校外 Off-campus: 已公開 available
論文名稱 Title |
台灣指形軟珊瑚Sinularia sp.天然物之研究 Studies on the Natural Products of the Formosan Soft Coral Sinularia sp. |
||
系所名稱 Department |
|||
畢業學年期 Year, semester |
語文別 Language |
||
學位類別 Degree |
頁數 Number of pages |
235 |
|
研究生 Author |
|||
指導教授 Advisor |
|||
召集委員 Convenor |
|||
口試委員 Advisory Committee |
|||
口試日期 Date of Exam |
2005-07-12 |
繳交日期 Date of Submission |
2005-08-16 |
關鍵字 Keywords |
海洋、天然物 marine, natural product |
||
統計 Statistics |
本論文已被瀏覽 5702 次,被下載 1345 次 The thesis/dissertation has been browsed 5702 times, has been downloaded 1345 times. |
中文摘要 |
針對台灣東北角鶯歌石附近海域所採集的軟珊瑚Sinularia sp.所具有的化學成分研究中,共分離出十二個天然化合物,分別為sinularioperoxides A-D(1-4)、sinulariolins A-D(5-8)、1a,3b-Di-hydroxy-24-methylencholesta-5,9-diene(9)、(3S)3,7-Dimethyl-nona-6,8-dienoic acid(10)、(2¢S)-Ethyl(5¢E)-5-(2¢,6¢-dimethylocta-5¢,7¢-dienyl)furan-3-carboxylate(11)、3'R,4'-((2R,4S)-2-Hydroxy-4-acetoxy-2,6,6-trimethyl-cyclohexylidene)but-3'-en-2'-one(12),其中十一個為新發現的天然化合物(1-11),而化合物12曾在藻類和植物中被發現。化合物(1-12)之化學結構是以各種光譜(1D NMR、2D NMR、IR、MS、UV)資料確立。 |
Abstract |
The chemical constituents of EtOH extracts of the soft coral Sinularia sp. have led to the isolation of nature compounds(1-12),sinularioperoxides A-D(1-4), sinulariolins A-D(5-8), 1a,3b-Dihydroxy-24-methylencholesta-5,9-diene(9),(3S)-3,7-Dimethyl-nona- 6,8-dienoicacid(10), (2¢S)-Ethyl(5¢E)-5-(2¢,6¢-dimethylocta-5¢,7¢-dienyl)furan-3-carboxylate(11), and one know metabolite, 3'R,4'-((2R, 4S)-2-hydroxy-4-acetoxy-2,6,6-trimethyl-cyclohexylidene)but-3'-en-2'-one(12), respectively. Compounds 1-11 are new and 12 is a know metabolite, which had been isolated from the brown alga and the plant. The structures of 1-12 were elucidated by the interpretation of spectroscopic data(UV, MS, IR, 1D and 2D NMR). |
目次 Table of Contents |
中文摘要 1 英文摘要 2 壹、緒論 一、前言 5 二、研究動機 6 三、過去相關研究概要 (一)、具有cyclic peroxide的sesquiterpene化合物文獻回顧 7 (二)、Valerenane type skeleton化合物文獻回顧 13 (三)、Eudesmane sesquiterpenes化合物文獻回顧 19 (四)、Sterols type skeleton具雙鍵D5,6、D9,11的化合物 文獻回顧 22 (五)、Furanosesquiterpenes 文獻回顧 24 貳、實驗程序與方法 一、生物樣品採集時間、地點與分類地位 26 二、萃取與分離純化步驟 27 三、實驗器材與溶劑 28 參、細胞毒殺活性測試 一、生物活性測試 30 二、實驗採用之癌細胞株 32 肆、實驗結果與討論 一、軟珊瑚Sinularia sp.化合物之結構解析 (一)、Sinularioperoxide A (1)之結構解析 33 (二)、Sinularioperoxide B (2)之結構解析 58 (三)、Sinularioperoxide C (3)之結構解析 72 (四)、Sinularioperoxide D (4)之結構解析 88 (五)、Sinulariolin A (5)之結構解析 102 (六)、Sinulariolin B (6)之結構解析 115 (七)、Sinulariolin C (7)之結構解析 131 (八)、Sinulariolin D (8)之結構解析 148 (九)、1a,3b-Dihydroxy-24-methylencholesta-5,9-diene (9) 163 (十)、(3S)-3,7-Dimethyl-nona-6,8-dienoic acid (10) 178 (十一)、(2¢S)-Ethyl(5¢E)-5-(2¢,6¢-dimethylocta-5¢,7¢- dienyl)furan-3-carboxylate (11) 191 (十二)、3'R,4'-((2R,4S)-2-Hydroxy-4-acetoxy-2,6,6-tri- methyl-cyclohexylidene)but-3'-en-2'-one (12) 205 伍、結論 217 陸、參考文獻 219 |
參考文獻 References |
1.Yasuyuki, H.; Satoshi, T.; Junya, M.“Antimicrobial sesquiterpene from damaged Rosa rugosa leaves.”Phytochemistry 1989, 28, 425- 430. 2.Yasuyuki, H.; Satoshi, T.; Junya, M.“Rugosal A and related carotane sesquiterpenes in the glandular trichome exudate of Rosa rugosa.”Phytochemistry 1992, 31, 779-782. 3.Yasuyuki, H.; Satoshi, T.; Junya, M. Agric.Biol.Chem. 1991, 55, 1049 -1053. 4.Yasuyuki, H.; Satoshi, T.; Junya, M.“Six sesquiterpenoids from glandular trichome exudates of.”Phytochemistry 1994, 35, 325-330. 5. Sanz, J.F.; Marco, J. A. “Sesquiterpene lactones from Artemisia caerulescens Subsp. gargantae”Phytochemistry 1990, 29, 2913-2917. 6. Dominguez, X. A.; Verde, S. J.; Guerra, R. N. E.; Ellenmaurer, E.; Jasmin, J. “A nor-diterpene and other constituents from Isocoma coronopifolia. ” Phytochemistry 1986, 25, 2893-2895. 7. Marco, J. A.; Sanz, J. F.; Enrique, F.; Jasmin, J.; Johann, L. “New oxygenated eudesmanolides from artemisia herba-alba.” Tetrahedron 1990, 46, 7941-7950. 8. Ngo, K. S.; Wong, W. T.; Brown, G. D. “Muurolane Sesquiterpenes from Illicium tsangii.”J. Nat. Prod. 1999, 62, 549-553. 9. Fumihiro, N.; Yoshinori, A. “Sesqui- and diterpenoids from two Japanese and three European liverworts.” Phytochemistry 2001, 56, 347-352. 10. Hideji, I.; Hiroshi, M.; Takeshi, K.; Kinzo, W.; Yoichi, I. “Novel Sesquiterpenes from Alpinia intermedia .” Chem. Pharm. Bull. 1987, 35, 2860-2868. 11. Yoshiaki, T.; Yoshie, T.; Megumi, A.; Osamu, N.; Takeshi, T.; Kensuke, K.; Kirn, H. S.; Yusuke, W.; Masatake, N.; Yoshiteru, O. “Novel Guaiane Endoperoxides, Nardoguaianone A–D, from Nardostachys chinensis Roots and their Antinociceptive and Antimalarial Activities.” Tetrahedron 2000, 56, 7673-7678. 12. Hideji, I.; Hiroshi, M.; Kenji, O.; Kinzo, W.; Yoichi, I. “Novel Guaiane- and Secoguaiane- type Sesquiterpenes from Alpinia japonica.” Chem. Pharm. Bull. 1987, 35, 2849-2859. 13. Jakupovic, J.; Tan, R. X.; Bohlmann, F.; Jia, Z. J.; Huneck, S. “Prenylated coumarates from Artemisia Xanthochroa.”Phytochemistry 1990, 29, 3683-3685. 14. Barrero, A. F.; Herrador, M. M.; Quilez, J. F.; Ramon ,A.M.; Dolores,P.; Garin, J. A.; Graralos, D. G.; Simmonds. M.S.J.; Blaney, W.M. “Bioactive sesquiterpenes from Santolina rosmarinifolia subsp. Canescens. A conformational analysis of the germacrane ring.” Phytochemistry 1999, 51, 529-542. 15. Ferdinand, B.; Ulrich, F.“Isofukinone, an eremophilane from Ligularia speciosa.”Phytochemistry 1980, 19, 2471-2472. 16. Ruecker, G.; Schenkel, E. P.; Manns, D.; Mayer, R.; Heiden, K.; Heinzmann, B. M. Planta Med. 1996, 62, 565-566. 17. Sy, L. K.; Brown, G. D.“Oxygenated bisabolanes from Alpinia densibracteata.”Phytochemistry 1997, 45, 537-544. 18. Fumihiro, N.; Makoto, S.; Shigeru, T.; Yoshinori, A.“New acorane- and cuparane-type sesqui- and new labdane- and seco-labdanne-type diterpenoids from the Japanese liverwort Jungermannia infusca (Mitt.) Steph.”Tetrahedron 1999, 55, 9117-9132. 19. Ulrich, L.; Gunther, B.; Hans, B. “Diterpene malonates and other terpenes from Nardia succulenta and N. scalaris.”Phytochemistry 1993, 33, 1173-1180. 20. Fumihiro, N.; Makoto, S.; Shigeru, T.; Yoshinori, A. “Sesqui- and Diterpenoids from the Japanese Liverwort Jungermannia infusca.” J. Nat. Prod. 2001, 64, 1309-1317. 21. Fumihiro, N.; Makoto, S.; Shigeru, T.; Yoshinori, A. “New sesqui- and diterpenoids from the Japanese Liverwort Jungermannia infusca.”Chem. Pharm. Bull. 1998, 46, 1184-1185. 22. Zhang, L.; Zhou, W. S.; Xu, X. X. “A New Sesquiterpene Peroxide(Yingzhaosu C) and Sesqutiterpenol(Yingzhaosu D) from Artabotrys unciatus.”J. Chem. Soc. Chem. Commun. 1988, 8, 523-524. 23. Tattje; Bos;“Valeranone, valeranal and vitispirane in the leaf oil of Liquidambar styraciflua.”Phytochemistry 1979, 18, 876. 24. Francois, G.; Philippe, C.; Ilias, K.“Essential oils from normal and hairy roots of Valeriana officinalis var. sambucifolia.”Phytochemistry 1995, 40, 1421-1424. 25. Seebeck, S. Justus Liebigs Ann. Chem. 1957, 603, 158, 165, 168. 26. Bos, R.; Hendriks, H.; Bruins, A. P.; Kloosterman, J.; Sipma, G.“Isolation and identification of valerenane sesquiterpenoids from Valeriana officinalis.” Phytochemistry 1986, 25, 133-136. 27. Ferdinand, B.; Michael, L. Chem. Ber. GE; 1980, 113, 2410-2423. 28. Claudia, P.; Koenig, W. A.; Hermann, M.“Pacifigorgianes and tamariscene as constituents of Frullania tamarisci and Valeriana officinalis.”Phytochemistry 2001, 57, 307-314. 29. Komarova, E. L.; Tsybul'ko, N. S.; Sheichenko, V. I.; Khorlin, A. Ya.; Fonin, V. S.; Ivleva, Zh. Yu.; Popov, D. M. Pharm. Chem. J.(Engl. Transl.) 2000, 34, 536-539; KHFZAN; Khim. F. Zh.; RU; 2000, 34, 22 -24. 30. Yoshiteru, O.; Yasuko, H.; Hiroshi, H.“Structure of cyclokessyl acetate, a sesquiterpenoid of Valeriana fauriei ‘hokkai-kisso’ roots.” Tetrahedron Lett. 1986, 27, 1829-1832. 31. Motosama, K.; Tohru, Y.; Yoshimasa, K.; Masaru, K.; Isao, K. “Three new ent-Valerenane sesquiterpenes from an okinawan soft coral.”Chem. Pharm. Bull. 1982, 30, 3431-3434. 32. Peter, W.; Helga, M. W.; Wahlburg, H. C. Liebigs Ann. Chem. 1989, 307-308 33. Graziano, G.; Danielle, S.; Sandra, B.; Ines, M.; Francesco, P. Tetrahedron Lett. 2001, 42, 723-726. Hironobu, T.; Seiko, Y.; Shoichi, K.; Hiroshi, A.; Yoshiyasu, F. “Lignans and sequiterpenes from Magnolia praecocissima. ” Chem. Pharm. Bull. 2002, 50, 541-543. 34. Dharmaratne, H. R. W.; Nanayakkara, N. P. D.; Khan, I. A. Planta Med. 2002, 68, 661- 662. 35. Su, W. C.; Fang, J. M.; Cheng, Y. S. “Sesquiterpenes from leaves of Cryptomeria japonica.” Phytochemistry 1995, 39, 603-608. 36. Feliciano, A. S.; Manuel, M.; Marina, G.; Olmo, E. D.; Corral, J. M. “Sesquiterpenoids and phenolics of Pulicaria aludosa.”Phytochemistry 1989, 28, 2717-2722. 37. Kuo, Y. H.; Lo, J. M.; Chan, Y. F. J.Chin.Chem.Soc.(Taipei) 2002, 49, 427-432. 38. Tchuendem, M. H. K.; Mbah, J. A.; Apollinaire, T.; Ayafor, J. F.; Olov, S.; Okunjic, C. C.; Iwu, M. M.; Schuster, B. M.“Anti-plasmodial sesquiterpenoids from the African Reneilmia cincinnata.” Phytochemistry 1999, 52, 1095-1100. 39. Ahmed, A. A.; Jakupovic, J.; Bohlmann, F. “Dihydroxypallenone, A sesquiterpene with a new carbon skeleton from Pallenis spinosa.”Phytochemistry 1990, 29, 3355-3358. 40. Andres, G. G.; Antonio, M.; Buruaga, Antonio Saenz de; Buruaga, Juan Manuel Saenz de;“Sesquiterpenes from two subspecies of Sideritis varoi.”Phytochemistry 1985, 24, 97-102. 41. Sung, T. V.; Steffan, B.; Steglich, W.; Klebe G.; Adam G.“Sesquiterpenoids from the roots of Homalomena aromatica.”Phyto- chemistry 1992, 31, 3515-3520. 42. Andres, G. G.; Antonio, M.; Antonio, M.; Onorato, M. E.“Terpenoids from Sideritis varoi subs oriensis.”Phytochemistry 1986, 25, 2171- 2174. 43. Zhao, Yu; Yue, J.; Lin, Z.; Ding, J.; Sun, H.“Eudesmane sesquiterpenes from Laggera pterodonta.”Phytochemistry 1997, 44, 459-464. 44. Izbosarov, M. B.; Yusupova, I. M.; Abduazimov, B. Kh.; Tashkhodzhaev, B.; Vdovin, A.; Abdullaev, N. D. Chem. Nat. Compd.(Engl.Transl.) 1998, 34, 289-294; Khim. Prir. Soedin.; RU; 1998, 3, 320-326. 45. Guo, W.; Zhu, R. X.; Shi, Y. P.; Jia, Z. J. “New sesquiterpene and other constituents from Artemisia arenaria.”Indian J. Chem. Sect. B 1999, 38, 828-830. 46. Hironobu, T.; Seiko, Y.; Shoichi, K.; Hiroshi, A.; Yoshiyasu, F. Chem. Pharm. Bull. 2002, 50, 541-543. 47. Vijender, S.; Mohd, A. Indian J. Chem. Sect. B 2004, 43, 655-659. 48. Hilal et al. Egypt. J. Pharm. Sci. 1976, 17, 87-89. 49. Pandey, R.; Verma, R. K.; Singh, S. C.; Gupta, M. M. “4α-Methyl-24β-ethyl-5α-cholesta-14,25-dien-3β-ol and 24β- ethylcholesta-5, 9(11), 22E-trien-3β-ol, sterols from Clerodendrum inerme.”Phytochemistry 2003, 63, 415-420. 50. Bowden, B. F.; Coll, J. C.; Silva, E. D. de; Costa, M. S. L. de; Djura, P. J.; Mahendran M.; Tapiolas D. M. “Studies of Australian Soft Corals. XXXI Novel Furanosesquiterpenes from Several Sinularian Soft Corals(Coelenterata, Octocorallia, Alcyonacea)” Aust. J. Chem. 1983, 36, 371-376. 51. 戴昌鳳"台灣的珊瑚"台灣省政府教育廳科學教育資料叢書(ΧVIII) ,台灣省政府教育廳,中華民國78年。 52. Bayer, F. M. Proc. Biol. Soc. Wash. 1981, 94 (3), 902-947.(珊瑚分類) 53. Hiromitsu, T.; Tomotake, I.; Mariko, K.; Norio, A.; Dazy, L.; Nonato, M. G.“A new alkaloid, pandanamine; finding of an anticipated biogenetic intermediate in Pandanus amaryllifolius Roxb.” Tetrahedron Lett. 2001, 42, 2995-2996. 54. Guo, C. J.; Wu, L. C.; Zeng, L. M.; Su, J. Y.“Synthesis of polyhydroxysterols (III): synthesis and structural elucidation of 24-methylenecholest-4-en-3β,6α-diol.”Steroids 2002, 67, 1015- 1020. 55. Andras, T.; Pierre, D.“Furanophane Transannular Diels-Alder Approach to (+)-Chatancin: An Asymmetric Total Synthesis of (+)-Anhydrochatancin.”J. Org. Chem. 2003, 68, 6847-6852. 56. Tu, Yong Q.; Huebener, A.; Zhang, H.; Moore, Christopher J.; Fletcher, M. T.; Hayes, P.; Dettner, K.; Francke, W.; Christopher S. P.; William, K. Synthesis 2000, 13, 1956 – 1978. 57. Takahisa, S.; Jotaro, O.; Ryozo, S. Agric. Biol. Chem. 1983, 47, 869- 876. 58. Takeshi, Y.; Hideo, U.; Shinya, W.; Makoto, H.; Hiroyuki, M,; Toshimitsu, H.“Synthesis and odor of optically active trans-2,2,6-trimethyl-cyclohexyl methyl ketones and their related compounds.”Tetrahedron 2003, 59, 517-524. 59. Muto, S. E.; Masahiko, B.; Kenji, M.“Synthesis and Stereochemistry of the Four Himachalene-Type Sesquiterpenes Isolated from the Flea Beetle (Aphthona flava) as Pheromone Candidates.”Eur. J. Org. Chem. 2004, 9, 1946–1952 60. Parameswaran, P. S.; Naik, C. G.; Das, B.; Kamat, S. Y.; Bose, A. K.; Nair, M. S. R. “Constituents of the brown alga padina tetrastromatica (Hauck)-II”Indian J. Chem. Sect. B 1996, 35, 463–467. 61. Toshihiro, H.; Motoo, T.; Yoshinori, A. “Piscicidal sterol acylglucosides from Edgeworthia chrysantha.”Phytochemistry 1991, 30, 2927–2931. 62. Isoe, S.; Katsumura, S.; Hyeon, B. S.; Sakan, T.; “Biogenetic type synthesis of grasshopper ketone and loliolide and a possible biogenesis of allenic carotenoids.”Tetrahedron Lett. 1971, 16, 1089–1092. |
電子全文 Fulltext |
本電子全文僅授權使用者為學術研究之目的,進行個人非營利性質之檢索、閱讀、列印。請遵守中華民國著作權法之相關規定,切勿任意重製、散佈、改作、轉貼、播送,以免觸法。 論文使用權限 Thesis access permission:校內外都一年後公開 withheld 開放時間 Available: 校內 Campus: 已公開 available 校外 Off-campus: 已公開 available |
紙本論文 Printed copies |
紙本論文的公開資訊在102學年度以後相對較為完整。如果需要查詢101學年度以前的紙本論文公開資訊,請聯繫圖資處紙本論文服務櫃台。如有不便之處敬請見諒。 開放時間 available 已公開 available |
QR Code |