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論文名稱 Title |
綠島產笙珊瑚之化學成分研究 Chemical Constituents of formosan Stolnifer Tubipora musica Linnaeus |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
163 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2001-06-09 |
繳交日期 Date of Submission |
2001-06-14 |
關鍵字 Keywords |
笙珊瑚 tubipora |
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統計 Statistics |
本論文已被瀏覽 5616 次,被下載 2304 次 The thesis/dissertation has been browsed 5616 times, has been downloaded 2304 times. |
中文摘要 |
中文摘要 綠島產笙珊瑚(Tubipora musica Linnaeus)之二氯甲烷層粗萃物,層析分離後得到九個sesquiterpenoids化合物,分別為GN32-17 (1)、 GN32-32(2)、GN32-66(3)、GN32-82(4)、GN32-83(5)、GN32-91(6)、GN32-94(7)、GN32-97(8)及GN32-98(9)。其中GN32-17(1)、GN32-32(2)、GN32-66(3)、GN32-91(6)、GN32-97(8)及GN32-98(9)為新化合物,且GN32-17(1)、GN32-66(2)及GN32-98(9)為首次在天然界中發現的新骨架,GN32-83 (5) 及GN32-94 (7) 為之前利用反應而得的化合物,而在此為第一次從天然物中發現的化合物。GN32-82(4)為已知的化合物。 |
Abstract |
Abstract Chromatographic separation of methylene chloride extract of Formosan stolonifer Tubipora musica Linnaeus (collected at Green Island) led to the isolation of nine sesquiterpenoids, GN32-17 (1), GN32-32 (2), GN32-66 (3), GN32-82 (4), GN32-83 (5), GN32-91 (6), GN32-94 (7), GN32-97 (8), and GN32-98 (9). Compounds 1, 2, 3, 6, 8, and 9 were new compounds . Compounds 4, 5, and 7 were known compounds. Compounds 1, 3, and 9 were new skeletons. |
目次 Table of Contents |
目錄 一、前言…………………………………………………1 二、Stolonifer目珊瑚之化學成分研究回顧…………………..2 三、材料之鑑定與採集………………………………………...27 四、笙珊瑚之分類地位………………………………………...27 五、化學成分之萃取與分離……………………………………28 (1) 、GN32-17(1)之分離純化………………….…..31 (2) 、GN32-32(2)之分離純化……………………...33 (3) 、GN32-66(3)之分離純化……………………...36 (4) 、GN32-82(4)之分離純化……………………...38 (5) 、GN32-83(5)之分離純化………………………41 (6) 、GN32-91(6)之分離純化………………………44 (7) 、GN32-94(7)之分離純化………………………46 (8) 、GN32-97(8)之分離純化………………………48 (9) 、GN32-98(9)之分離純化………………………51 六、結構解析 (1)、GN32-17(1)之結構解析……………………….54 (2)、GN32-32(2)之結構解析……………………….65 (3)、GN32-66(3)之結構解析………………..……...76 (4)、GN32-82(4)之結構解析…………………….…87 (5)、GN32-83(5)之結構解析……………………….98 (6)、GN32-91(6)之結構解析……………………...109 (7)、GN32-94(7)之結構解析……………………...120 (8)、GN32-97(8)之結構解析………………….…..131 (9)、GN32-98(9)之結構解析……………………...142 七、 結論………………………………………………153 八、參考文獻…………………………………………..154 九、儀器及材料………………………………………..162 圖 表 目 錄 圖次 頁次 圖一、綠島產笙珊瑚之萃取及分離流程圖………………..30 圖二、GN32-17(1)之1H-NMR圖譜…………………….57 圖三、GN32-17(1)之13C-NMR圖譜……………………58 圖四、GN32-17(1)之HSQC圖譜……………………….59 圖五、GN32-17(1)之COSY圖譜……………………….60 圖六、GN32-17(1)之HMBC圖譜……………………….61 圖七、GN32-17(1)HMBC之 correlations圖……………62 圖八、GN32-17(1)之NOESY圖譜………………………63 圖九、GN32-17(1)NOESY之 correlations圖………..…64 圖十、GN32-32(2)之1H-NMR圖譜……………………..68 圖十一、GN32-32(2)之13C-NMR圖譜…………………..69 圖十二、GN32-32(2)之HSQC圖譜………………………70 圖十三、GN32-32(2)之COSY圖譜………………………71 圖十四、GN32-32(2)HMBC之圖譜………………………72 圖十五、GN32-32(2)HMBC之 correlations圖…………..73 圖十六、GN32-32(2)之NOESY圖譜……………………..74 圖十七、GN32-32(2)之NOESY之 correlations圖………75 圖十八、GN32-66(3)之1H-NMR圖譜……………………79 圖十九、GN32-66(3)之13C-NMR圖譜…………………..80 圖二十、GN32-66(3)之HSQC圖譜……………………...81 圖二十一、GN32-66(3)之COSY圖譜……………………82 圖二十二、GN32-66(3)之HMBC圖譜……………………83 圖二十三、GN32-66(3)HMBC之 correlations圖………..84 圖二十四、GN32-66(3)之NOESY圖譜…………………..85 圖二十五、GN32-66(3)NOESY之 correlations圖………..86 圖二十六、GN32-82(4)之1H-NMR圖譜………………….90 圖二十七、GN32-82(4)之13C-NMR圖譜………………….91 圖二十八、GN32-82(4)之HSQC圖譜…………………..…92 圖二十九、GN32-82(4)之COSY圖譜……………………..93 圖三十、GN32-82(4)之HMBC圖譜……………………….94 圖三十一、GN32-82(4)HMBC之 correlations圖………...95 圖三十二、GN32-82(4)之NOESY圖譜………………..…96 圖三十三、GN32-82(4)NOESY之 correlations圖……….97 圖三十四、GN32-83(5)之1H-NMR圖譜……………..…101 圖三十五、GN32-83(5)之13C-NMR圖譜……………….102 圖三十六、GN32-83(5)之HSQC圖譜…………………..103 圖三十七、GN32-83(5)之COSY圖譜…………………..104 圖三十八、GN32-83(5)之HMBC圖譜…………………..105 圖三十九、GN32-83(5)HMBC之 correlations圖……….106 圖四十、GN32-83(5)之NOESY圖譜…………………….107 圖四十一、GN32-83(5)NOESY之 correlations圖………108 圖四十二、GN32-91(6)之1H-NMR圖譜………………….112 圖四十三、GN32-91(6)之13C-NMR圖譜…………………113 圖四十四、GN32-91(6)之HSQC圖譜……………………..114 圖四十五、GN32-91(6)之COSY圖譜……………………..115 圖四十六、GN32-91(6)之HMBC圖譜…………………..116 圖四十七、GN32-91(6)HMBC之 correlations圖……….117 圖四十八、GN32-91(6)之NOESY圖譜…………………118 圖四十九、GN32-91(6)NOESY之 correlations圖……..119 圖五十、GN32-94(7)之1H-NMR圖譜………………..…123 圖五十一、GN32-94(7)之13C-NMR圖譜……………….124 圖五十二、GN32-94(7)之HSQC圖譜…………………..125 圖五十三、GN32-94(7)之COSY圖譜…………………..126 圖五十四、GN32-94(7)之HMBC圖譜…………………..127 圖五十五、GN32-94(7)HMBC之 correlations圖……….128 圖五十六、GN32-94(7)之NOESY圖譜………………….129 圖五十七、GN32-94(7)NOESY之 correlations圖………130 圖五十八、GN32-97(8)之1H-NMR圖譜………………..134 圖五十九、GN32-97(8)之13C-NMR圖譜……………….135 圖六十、GN32-97(8)之HSQC圖譜……………………..136 圖六十一、GN32-97(8)之COSY圖譜…………………..137 圖六十二、GN32-97(8)之HMBC圖譜………………….138 圖六十三、GN32-97(8)HMBC之 correlations圖………139 圖六十四、GN32-97(8)之NOESY圖譜…………………140 圖六十五、GN32-97(8)NOESY之 correlations圖………141 圖六十六、GN32-98(9)之1H-NMR圖譜…………………145 圖六十七、GN32-98(9)之13C-NMR圖譜………………..146 圖六十八、GN32-98(9)之HSQC圖譜……………………147 圖六十九、GN32-98(9)之COSY圖譜……………………148 圖七十、GN32-98(9)之HMBC圖譜……………………..149 圖七十一、GN32-98(9)HMBC之 correlations圖……….150 圖七十二、GN32-98(9)之NOESY圖譜………………….151 圖七十三、GN32-98(9)NOESY之 correlations圖……..152 |
參考文獻 References |
八、參考文獻 1 . J. C. Braekman, D. Daloze, A. Dupont, and B. Tursch, “Chemical Studies of Marine Invertebrates-XLIII”, Tetrahedron, 1981, 37, 179-186. 2 . M. Kobayashi, B. W. Son, M. Kido, Y. Kyogoku, and I. Kitagawa, “Clavukerin A, a New Trinor-guaiane Sesquiterpene from the Okinawan Soft Coral Clavularia koellikeri.”, Chem. Pharm. Bull., 1983, 31, 2160-2163. 3 . R. R. Izac, and W. Fenical, “ Inflatene, an Ichthyotoxic C12 Hydrocarbon From the Stoloniferan Soft Coral Clavularia Inflata Var. Luzoniana.”, Tetrahedron Letters, 1984, 25, 1325-1328. 4 . M. Kobayashi, B. Wha Son, Y. Kyogoku, and I. Kitagawa, “Clavukerin C, a New Trinor- Guaiane Sesquiterpene Having a Hydroperoxy Function, from the Okinawan Soft Coral Clavularia koellikeri.”, Chem. Pharm. Bull., 1984, 32, 1667-1670. 5 . T. Kusumi, T. Hamada, M. Hara, M. O. Ishitsuja, H. Ginda, and H. Kakisawa, “Structure and Absolute Configuration of Isoclavukerin A, a Component from an Okinawan Soft Coral”, Tetrahedron Letter”, 1991, 2019-2022. 6. M. Yasumoto, K. Mada, T. Ooi, and T. Kusumi, “New Terpenoid Component from the Volatile Oils of the Soft Coral Clavularia viridis and Sarcophyton Acutangulum.”, J. Nat. Prod., 2000, 63, 1534-1536. 7. B. F. Bowden, J. C. Breakman, J. C. Coll, and S. J. Mitchell, “Studies of Australian Soft Corals. A New Sesquiterpene Furan from Soft Corals of the Eamily Xeniidae and an Exzmination of Clavularia inflata from North Queensland Waters.”, Aust. J. Chem, 1980, 33, 927-932. 8. H. Kikuchi, and Y. Tsukitani, “Clavulones, New Type of Prostanoids from the Stolonifer Clavularia viridis Quoy and Gaimard.”, Tetrahedron Letters, 1982, 23, 5171-5174. 9. H. Kikuchi, and Y. Tsukitani, “clavulones, New Type of prostanoids from the stolonifer Clavularia viridis Quoy and Gaimard.”, Tetrahedron Letters, 1982, 49, 5171-5174. 10. H. Kikuchi, and Y. Tsukitani, “Absolute Stereochemistry of New Prostanoids Clavulone I, II, and III, from clavularia viridis Quoy and Gaimard.”, Tetrahedron Letters, 1986, 24, 1549-1552. 11. K. Iguchi, and Y. Yamada, “Novel C-20-Oxygenated Prostanoids, 20-Acetoxyclavulones, from the Stolonifer Clavularia viridis Quoy and Gaimard.”, Tetrahedron Letters, 1983, 24, 4433-4434. 12. M. Endo, M. Nakagawa, Y. Hamamoto, and T, Nakanishi, ”Clavularins, a New Class of Cytotoxic Compounds Isolated from the Soft Coral, Clavularia koellikeri.”, J. Chem. Soc. Commun, 1983, 322-323. 13. M. Kobayashi, B. w. Son, T. Fujiwara, Y. Kyogoku, and I, Kitagawa, “neodolabelline, a Methyl Methyl Migrated Dolabellane- Type Diterpene from the Okinawan Soft Coral Clavularia koellikeri.”, Tetrahedron Letters, 1984, 25, 5543-5546. 14. M. Kobayashi, N. K. Lee, B. W. Son, K. Yanagi, Y. Kyogoku, and I. Kigatawa, “Stoloniferone-A, -B, -C, and –D, Four the Okinawan Soft Coral Clavularia viridus”, Tetrahedron Letters, 1984, 25, 5925-5928. 15. Y. Yamada, “Identification of a New Eicosanqid from in Vitro Biosynthetic Experiments with Clavularia viridis. Implications for the Biosynthesis of Clavulones.”, Tetrahedron Letters, 1985, 26, 4171-4174. 16. K. Iguchi, S. Kaneta, K. Mori, Y. Yamada, A. Honda, and y. Mori, “Chlorovulones, New Halogenated Marine Prostanoids with an Antitumor Activity from the Stolonifer Clavularia viridis Quoy and Gaimard”, Tetrahedron Letters, 1985, 26, 5787-5790. 17. K. Iguchi, S. Kaneta, K. Mori, Y. Yamada, A. Honda, and Y. Mori, “Bromovulone I and Iodovulone I, Unprecedented Brominated and Iodinated Marine Prostanoids with Antitumour Activity Isolated from the Japanese Stolonifer Clavularia viridis Quoy and Gaimard.”, J. Chem. Soc., Chem. Commun., 1986, 981-982. 18. M. Kobayashi, B. W. Son, Y. Kyogoku, and I. Kitagawa, “Kericembrenolides A, B, C, D, and E, Five New Cytotoxic Cembrenolides from the Okinawan Soft Coral Clavularia koellikeri”, Chem. Pharm. Bull, 1986, 34, 2306-2309. 19. K. Iguchi, K. Mori, M. Suzuki, H. Takahashi, and Y. Yamada, “New Marine Furanosesquiterpenoids, Tubipofuran and 15-Acetoxytubipofuran from the Stolonifer tubipora musica Linnaeus.”, Chemistry Litters, 1986, 1789-1792. 20. K. Iguchi, K. Mori, M. Matsushima, and Y. Yamada, “Spirotubipolide, a New Marine Sesquiterpenoid from the Stolonifer Tubipora musica Linnaeus.”, Chem. Pharm. Bull, 1987, 35, 3531-3533. 21. K. Kori, K. Iguchi, N. Yamada, and Y, Yamada, “Stolonidiol, a New Marine Diterpenoid with a Strong Cytotoxic Activity from the Japaese Soft Coral”, Tetrahedron Letters, 1987, 28, 5679-5676. 22. K. Iguchi, S. Kaneta, K. Mori, and Y. Yamada, “A New Marine Prostanoid with an Antiproliferative Activity from the Stolonifer Clavularia viridis Quoy And Gaimard”, Chem. Pharm. Bull, 1987, 35, 4375-4376. 24 . K. Mori, K. Iguchi, N. Yamada, Y. Yamada, and Y. Inouye,”Bioactive Marine Ditterpenoids from Japanese Soft Coral of Clavularia sp.”, Chem. Pharm. Bull., 1988, 36, 2840-2852. 25 . W. Inman and P. Crews, “The Structure and Conformational Properties of a Cembranolide Diterpene from Clavularia violacea”, J. Org. Chem., 1989, 54, 2526-2529. 26. T. Natori, H. Kawai, and N. Fusetani, “Tubiporein, a Novel Diterpene from a Japanese Soft Coral Tubipora sp”, Tetrahedron Letters., 1990, 31, 689-690. 27 . J. Su, Y. Zhong, and K. Shi, “Clavudiol A and Clavirolide A, Two Marine Dolabellane Diterpenes from the Soft Coral Clavularia viridis”, J. Org. Chem., 1991, 56, 2337-2344. 28 . J. Su, Y. Zhong, and L. Zeng, “Four Novel Diterpenoids: Clavirolides B, C, D, and E from the Chinese Soft Coral Clavularia viridis”, J. Nat. Prod., 1991, 54, 380-385. 29. B. J. Baker, and P. J. Scheuer, “The Punaglandins: 10-Chloroprostanoids from the Octocoral telesto Riisei”, J. Nat. Prod, 1994, 57, 1346-1353. 30 . K. Iguchi, M. Iwashima, and K. Watanabe, “Stoloniolide I and II, New Marine Lactonic Steroids with an Unprecedented 1,10-Secoergostane Skeleton, Isolated from the Okinawan Soft Coral, Clavularia viridis”, Chemistry Letters., 1995, 1109-1110. 30. K. Iguchi, M. Iwashlma, and K. Watanabe, “Clavulactones, New Marine Prostanoids with a γ-lactonic Moiety in the α-side-chain from the Okinawan Soft Coral, Clavularia viridis.”, J. Nat. Prod., 1995, 58, 790-793. 32. K. Watanabe, M. Iwashima, and K. Iguchi, “New Marine Prostanoid Carboxylate Salts from the Okinawan Soft Coral Clavularia viridis”, J. Net. Prod., 1996, 59, 980-982. 33. M. Iwashima, K. Watanabe, and K. Iguchi, “New Marine Prostanoids, Preclavulone lactone, from the Okinawan Soft Coral Clavularia viridis”, Tetrahedron Letters, 1997, 38, 8319-8322. . 33. M. Iwashima, K. Okamoto, and K. Iguchi, ”Clavirins, a New Type of Marine Oxylipins with Growth- Inhibitory Activity from the Okinawan Soft Coral, Clavularia viridis.”, Tetrahedron Letters, 1999, 40, 6455-6459. 35. M. Iwashima, K. Okamoto, Y. Mayai, and K. Iguchi, “4-Epiclavulones, New Marine from the Okinawan Soft Coral, Clavularia viridis.”, Chem. Pharm. Bull, 1999, 47, 884-886. 36. M. Iwashima, K. Okamoto, F. Konno, and K. Iguchi, “New Marine Prostanoids from the Okinawan Soft Coral, Clavuloria viridis”, J. Nat. Prod., 1999, 62, 352-354. 37 . M. Iwashima, K. Nara, K. Iguchi, “New Marine Steroids, Yonarasterols, Isolated from the Okinawan Soft Coral, Clavularia viridis”, Steroids., 2000, 65, 130-137. 38 . M. Iwashima, Y. Matsumoto, H. Takahashi, and K. Iguchi, “New marine Cembrane-type Diterpenoids from the Okinawan Soft Coral Clavularia koellikeri”, J. Nat. Prod., 2000, 63, 1647-1652. 39. N. Goren and A. Ulubelen, “Oxenpine Derivatives from the Roots of Smyrnium rotundifolium”, Phytochemistry, 1985, 24,3051-6052. 40. N. Goren and A. Ulubelen, “Glechomanolides and Eudesmanolides from Smyrnium perfoliatum”, Phytochemistry, 1987, 26, 2585-2587. 41. W. Y. Tsui and G. D. Brown, “Cycloeudesmanolides from Sarcandra Glabra”, Phytochemistry, 1996, 43, 819-821. 42. C. L. Cantrell, L. Abate, F. R. Fronczek, S. G. Franzblau, L. Quijano, and N. H. Fischer, “Antimycobacterial Eudesmanolides from Inula Helenium and Rudbeckia subtomentosa”, Planta Med, 1999, 65, 351-355. 43. A. Ulubelen, N. Goren, F. Bohlmann, J. Jakupovic, M. Grenz, and N. Tanker, “Sesquiterpene Lactones from Smyrnium cordifolium”, Phytochemistry, 1985, 24, 1305-1308. |
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