(18.206.12.76) 您好!臺灣時間:2021/04/23 09:56
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果

詳目顯示:::

我願授權國圖
: 
twitterline
研究生:王復興
研究生(外文):Fu-Shing Wang
論文名稱:海洋天然物Neolemnane及NeolemnaneAcetate之全合成研究與酞靑及電致色變光電材料之合成與應用
論文名稱(外文):Synthetic Studies Marine Natural Products of Neolemnane and Neolemnane Acetate, Sythesis and Application of Some Phthalocyanines and Organic Electrochromes
指導教授:劉行讓
指導教授(外文):Hsing-Jang Liu
學位類別:博士
校院名稱:國立清華大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2003
畢業學年度:91
語文別:中文
論文頁數:258
中文關鍵詞:天然物電致色變光碟
外文關鍵詞:NeolemnaneNeolemnanyl acetatephthalocyanineelectrochromicelectrochromism
相關次數:
  • 被引用被引用:0
  • 點閱點閱:117
  • 評分評分:系統版面圖檔系統版面圖檔系統版面圖檔系統版面圖檔系統版面圖檔
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:0
本論文共分三部份:第一部份報導倍半萜 (sesquiterpenoids) 天然物neolemnane (1)及neolemnane acetate (2)之合成研究,此合成之主要策略乃利用化合物36為親二烯基進行Diels-Alder環化反應。此化合物之氰基除了增加親二烯基的活性,促使快速的建立天然物所具備的八-六環骨架並有效的控制立體化學外,亦可經由還原去氰烷化反應引進C-1的甲基。在這一部份的研究、我們合成出重要的中間體化合物72,可作為後續全合成之推進基礎。
第二部份報導可以醇類溶劑溶解之phthalocyanine分子的合成方法及其在光紀錄材料上的應用。本研究、以廉價的鋁金屬離子作為大環的核心,並引入氫氧基作為軸向取代基,減低phthalocyanine分子間的重疊性,增加對醇類溶劑之溶解度。經塗佈工程,以銀為反射層,化合物135作為紀錄層,可製作成24倍速寫入之碟片。紀錄層加入化合物145可分散化合物 135對雷射能量的吸收,提升碟片的穩定性,可製作成32倍速寫入之金黃色碟片。
第三部份報導合成新型的互補式電致色變材料化合物210、211、212、213、214、215。本研究中,經CV分析篩選出陰極化合物211、213與陽極化合物214,在電化學性質上有良好的氧化還原循環電位,並互相搭配製作成兩個電致色變元件,進行光電測試。其一以1.5 V驅動後呈現藍綠色,另一則呈現褐色。元件的變色與退色都相當迅速,元件壽命亦能達到10000次以上之氧化還原循環變色次數。
Abstract
The first chapter of this thesis describes the synthetic efforts towards the total synthesis of naturally occurring sesquiterpenes neolemnane (1) and neolemnane acetate (2) based on the Diels-Alder cycloaddition. Activated enone 36 was found to be a highly reactive dienophile and the resulting angular nitrile moiety, after serving as an activator, was readily replaced with a methyl group using a reductive methylation procedure previously developed in our laboratories. Subsequent functional group manipulations yielded bicyclic ketone 72,an advanced intermediate in our planned total synthesis strategy.
The second chapter details the synthesis of alcoholic soluble phthalocyanines and their application in optical memory devices. It was discovered that the incorporation of an aluminum atom as the metal center as well as the introduction of a hydroxy functionality effectively disrupted the intermolecular stracking tendencies of the parant molecules, thereby enhancing solubility. As an application, using a silver reflective surface and compound 135 as the recording surface, 24X cd-roms were produced in a coating process. Additionally, by doping the recording surface of 135 with compound 145, the stability of the resulting devices was enhanced. This is due to the effective dissipation of laser energy absorbed by 135 resulting from the introduction of compound 145. This higher stability allowed for the production of 32X recording devices as gold colored plates.
In the third chapter, the synthesis of new complementary electrochromic compounds 210, 211, 212, 213, 214 and 215 is described. For electrochemical studies with CV analysis, superior redox cycles were obtained for anodic compounds 211 and 213 and cathodic compound 214. Two electrochromic devices were fabricated with these compounds to study their photonic properties. One device showed blue color and the other displayed brown color after activating with a 1.5 V current. The response of both colour and bleaching reactions was quite swift. More than 1000 times of redox cycles could be obtained.
目錄
中文摘要…………………………………………………………………
英文摘要…………………………………………………………………
謝誌………………………………………………………………………
縮寫對照表………………………………………………………………
目錄………………………………………………………………………第一章 天然物Neolemnane與Neolemnanyl acetate 之合成研究……
1.1 緒論………………………………………………..………
1.2 研究構想……………………………………..…………...
1.3 結果討論………………………………………………….
合成路徑一……………………………………………….
合成路徑二…………………………………………….…
合成路徑三…………………………………………….…
1.4 結論……………………………….………………………
1.5 實驗步驟與光譜資料………………………..…………..
1.5.1 一般實驗方法………………………………………….
1.5.2 實驗步驟……………………………………………….
1.6 參考文獻…………………………………….………….
第二章 Phthalocyanine之合成與應用……….………………………...
2.1緒論……………..…..….……………………………… 2.1.1 Phthalocyanine之簡介…………………...………….….
2.1.2 Phthalocyanine 的合成………………….………….…..
2.2 Phthalocyanine之應用…………………………….…..….
2.3 研究構想……………………………………..……….….
2.4 逆合成分析………………………………………..….….
2.5 結果討論…………………..……………………………..
2.5.1 化合物135之合成…………………………………….
97
83
90
96
98
98
98
101
104
109
117
119
119
125
128
133
141
142
151
154
2.5.2 化合物135於CD-R之塗佈應用……………………….
2.6 結論……………………………………………………….
2.7實驗步驟與光譜資料………………………………….….
2.8 參考文獻………………………………………………….
第三章 電致色變化合物之合成與應用……………………………….
3.1 緒論……………………………………………………….
3.1.1電致色變系統簡介………………………………………
3.1.2電致色變材料……………………………………………
3.1.3電致色變元件的種類與組成……………………………
3.2 文獻回顧…………………………...……………………..
3.3 研究構想………………………………………………….
3.4 結果討論……………………...…………………………..
3.4.1 電致色變化合物之合成………………………………..
3.4.2 陽極化合物 (Viologen) 的電化學分析……………….
3.4.3 陰極化合物 (Hydrozone) 的電化學分析……………..
3.4.4 Viologen/Hydrozone互補式電致色變元件製作與光譜性質…………………………………………………….
3.5 結論………………………………...…………………….
3.6 實驗步驟與光譜資料……………………………………
3.7 參考文獻…………………………………………………
附錄……………………………………………………………………..
1.6 參考文獻
1. Izac, R. R.; Fenical, W.; Tagle, B.; Clardy, J. Tetrahedron 1981, 37, 2569.
2. Majetich, G.; Lowery, D.; Khetani, V.; Song, J. S.; Hull, K.; Ringold, C. J. Org. Chem. 1991, 56, 3988.
3. Ham, W. H., Ph.D. Thesis, The Ohio State University, 1986.
4. Renga, J. M.; Reich, H. J. Org. Synth. Coll. Vol. VII (1975-1979), P 23.
5. Hatch, R. P.; Shringarpure,; Weinred, S. M. J. Org. Chem. 1978, 43, 4172.
6. Fujimoto, Y., Tatsano, T. Tetrahedron Lett. 1976, 3325.
7. Zhu, J-L.; Shia, K-S.; Liu, H-J. Chem. Commun. 2000, 17, 1599 - 1600.
8. Yip, J., Ph.D. Thesis, The University of Alberta, 1996.
9. Shang, X.; Ph.D. Thesis, The University of Alberta, 1996.
10. Saito, S.; Ito, M.; Yamamoto, H. J. Am. Chem. Soc. 1968, 90, 4464.
11. Pasto, D. J.; Wojtkowski, P. W. J. Org. Chem. 1971, 36, 1790.
12. Kende, A. S.; Fludzinski, P. Org. Synth. Coll. Vol. VII (1981-1985), p208.
13. Liotta, D.; Barnum, R. P.; Zima, G.; Bayer, C.; Kezar, H. S. J. Org. Chem. 1981, 46, 2920.
14. Inukai, T.; Kojima, T. J. Org. Chem. 1966, 31, 1121.
15. House, H. O.; Lusch, M. J. J. Org. Chem. 1971, 36, 387.
16. Mihelich, E. D.; Eickhoff, D. J. J. Org. Chem. 1983, 48, 4135.
17. Ireland, R. E.; Thompson, W. J. J. Org. Chem. 1979, 44, 3041.
18. Baldwin, R. J. Org. Chem. 1989, 54, 5264.
19. Ryu, I.; Murai, S.; Hatayama, Y.; Sonoda, N. Tetrahedron 1981, 37, 2569.
20. Brown, H. C.; Grag, C. O.; Liu, K. T. J. J. Org. Chem. 1971, 36, 387.
21. Mehta, G.; Murthy, A. N.; Reddy, D. S.; Reddy, A. V. J. Am. Chem. Soc. 1986, 108, 3443.
22. Okawara, H.; Nakai, H.; Ohno, M. Tetrahedron Lett. 1982, 23, 1087.
23. Guijarro, A.; Yus, M. Tetrahedron 1994, 50, 3447.
24. Ono, N.; Yoshimura, T.; Saito, T.; Tamura, R.; Tanikaga, R.; Kaji, A. Bull. Chem. Soc. Jpn. 1979, 52, 1716.
2.8 參考文獻
1. Braun, A.; Tcherniaj, J. Ber Chem. 1907, 40, 2709.
2. Diesbach, H.; Weid, E. Helv. Chim. Acta 1927, 10, 886.
3. Cronshaw, C. J. T. Les, Phthalocyanines. Endeavour. 1942, 1, 79.
4. Dandridge, A. G.; Drescher, H. A.; Thomas, J. British Patent. 1929, 322, 169.
5. Linstead, R. P. J. Chem. Soc. 1934, 1016.
6. Linstead, R. P. J. Chem. Soc. 1934, 1022.
7. Lever, A. B. P. Advances in Inorg. Radiochem, 1965, 27, 27.
8. Moser, F. H.; Thomas, A. L. The Phthalocyanine, Volume 1: Properties, Boca, Raton, Floride: CRC Press, 1983.
9. Wohrle, D.; Eskes, M.; Shigehara, K.; Yamada, A. Synthesis 1993, 194.
10. Leznoff, C. C.; Hall, T. W. Tetrahedron lett. 1982, 23, 3023.
11. Thompson, J. A.; Murata, K.; Miller, D. C.; Standton, J. L.; Broderick, W. E.; Hoffman, B. M.; Ibers, J. A. Inorg. Chem. 1993, 32, 3546.
12. De Cian, A.; Moussavi, M.; Fischer, J.; Weiss, R. Inorg. Chem. 1985, 24, 3162.
13. Lowery, M. K.; Starshak, A. J.; Esposito, J. N.; Krueger, P. C.; Kennet, M. E. Inorg. Chem. 1965, 4, 128.
14. Hayashida, S.; Hayashi, N. Chem. Mater. 1991, 3, 92.
15. Hayashida, S.; Hayashi, N. Synthetic Metals 1991, 41, 1243.
16. Kovsher, E. I.; Solov’eva, L. I.; Mikhalenko, S. A.; Luk’yanets, E. A. Zhurnal Vsesoyuznogo Kihimiicheskogo Obshchestva im D. I. Mendeleeva, 1976, 21, 465.
17. Metz, J.; Schneider, O.; Hanack, M. Inorg. Chem. 1984, 23, 1065.
18. Hanack, M.; Metz, J.; Pawlowski, G. Chem. Beri. 1982, 115, 2836.
19. Hanack, M.; Meng, D. Y.; Beck, A. Sommerauer, M.; Subramanian, L. R. J. Chem. Soc., Chem Commum. 1993, 58.
20. Schmidt, A.; Chau, L. K.; Beck, A.; Armstrong, N. R. Phthalocyanine: Properties and Applications, Volumne 4, C. C. Leznoff and A. B. P. Lever, 1996, 307.
21. Pawlowski, G.; Hanack, M. Synthesis 1980, 287.
22. Mckeown, N. B.; Cook, M. J.; Thomson, A. J.; Harrison, K. J.; Daniel, M. F.; Richardson, R. M.; Roser, S. J. Thin Solid Films 1988, 159, 469.
23. Cook, M. J.; Dunn, A. J.; Harrison, K. J. J. Chem. Soc., Perkin Trans. I 1988, 2458.
24. Canon, J Patent 61165 1984.
25. Yagishita, T.; Okuyama, H.; Ikegami, K.; Narusawa, T. IEEE Transations on Industry Applications. 1984, 20, 1642.
26. Loutfy, R. O.; Hor, M. A.; Hsiao, C. K.; Baranyi, G. Kazmaier, P. Pure Appl. Chem. 1988, 60, 1047.
27. Kume, T.; Hayashi, S.; Yamamoto, K. Japanese Journal of Applied Physics Part 1- Regular Papers Short Notes & Review Papers, 1993, 32, 3486.
28. Murata, K.; Takahashi, K.; Hoffman, M. Appl. Phys. Lett. 1996, 68, 427.
29. Kume, T.; Hayashi, S.; Yamamoto, K. J. Appl. Phys. 1995, 34, 6448.
30. Zemtseva, L. I.; Titov, V. I.; Antipenko, V. R.; Ivasenko, V. L. U.S.S.R. Patent 1197928 1985.
31. Trynda, L.; Przywarska-Boniecka, H.; Kosciukiewicz, T. Inorg. Chim. Acta. 1987, 55, 135.
32. Gu, D. H.; Chen, Q. Y.; Tang, X. D.; Gan, F. X.; Shen, S. Y.; Liu, K.; Xu, H. J. Optical Communications. 1995, 121, 125.
33. Kock, Y. L.; Gorgon, E. U.S. Patent. 4529688. 1985.
34. Sato, T.; Miyazaki, M.; Sakamoto, M.; Motonori, A. U.S. Patent. 5283094 1990.
35. Sasakawa, T.; Kitagawa, N.; Koike, T. U.S. Patent. 5283094 1994.
36. Yanagisawa, S.; Tanaka, S.; Mtasui, F. U.S. Patent. 424171 1995.
37. Tomura, T.; Sato, T.; Sasa, N. U.S. Patent. 5677025 1997.
38. Yashiro, T.; U.S. Patent. 5789138. 1998.
39. Gould, Ken. J.; Hacker, N. P.; McOmie, J. F. W.; Perry, D. H. J. Chem. Soc., Perkin Trans.1 1980, 1834.
40. Drew, P. J. Chem. Soc, 1937, 26, 31.
41. Clelland, R. A.; Seaman, N. Esther, D.; James, M.; Branston, R. E. Can. J. Chem, 1985, 63, 121.
42. George, R. D.; Snow, A. W. J. Heterocycl. Chem. 1995, 32, 495-498.
43. Leznoff, C. C.; Hu, M; McArthur, C. R.; Qin, Y.; Lier, J. E. Can. J. Chem, 1994, 72, 1990-1998.
44. Leznoff, C. C.; Hu, M.; McArthur, C. R.; Qin, Y.; Lier, J. E. Can. J. Chem, 1994, 72, 1990-1998.
45. Kasuga, K.; Kawashima, M.; Asano, K.; Sugimori, T.; Abe, Kohji. Chem. Lett. 1996, 867.
46. Lee, C. H.; Ng, D. K.; Teltay, P. Tetrahedron Lett. 2002, 43, 4211 - 4214.
47. Liu, W.; Lee, C. H.; Li, H. W.; Lam, C. K.; Wang, J.; Mak, T. C.; Ng,
3.7參考文獻
1. Platt, J. R. J. Chem. Phys. 1961, 34, 862.
2. 葉時傑碩士論文, 國立清華大學, 1998.
3. 楊明長, “電致色變系統簡介,” 化工, 第40卷第2期, 1993, 64.
4. Mortimer, R. J. Chem. Soc. 1997, 26, 147.
5. Itaya, K.; Shibayama, K.; Akahshi, H.; Toshima, S. J. Appl. Phys. 1982, 53, 804.
6. Collins, G. S. E.; Schiffrin, D. J. J. Electroanal. Chem. 1982, 139, 335.
7. Collins, G. S. E.; Schiffrin, D. J. J. Electrochem. Soc. 1985, 132, 1835.
8. Rourke, F.; Crayston, J. A. J. Chem. Soc., Faraday Trans. 1993, 89, 295.
9. MacNeill, R.; Weiss, D. E.; Willist, D. Aust, J. Chem. 1965, 18, 477.
10. Diaz, A. F. Chem. Ser. 1981, 17, 145.
11. Lavey, G.; Emmertson, T. W. J. Phy. Chem. 1983, 87, 829.
12. Van Der Leest, R. E. J. Electroanal. Chem. 1973, 43, 257.
13. Kosower, E. M. An Introduction to Physical Organic Chemistry, Wiley, New York. 1968.
14. Mortimer, R. J.; Monk, PM. S.; Rosseinsky, D. R. “Electrochromism Fundamentals and Application”. Weinheim, New York, 1995.
15. Leventis, N. McGraw-Hill Yearbook of Science and Technology in 1994, McGraw-Hill, New York, 1994, p156.
16. Stepp, J.; Schlenoff, J. B. J. Electrochem. Soc. 1997, 144, 1155.
17. Brown, G. H. “Photochromism”. Wiley Interscience, New York, 1971.
18. Inoue, E.; Kawaziri, K. Izawa, A. J. Appl. Phys. 1977, 16, 2065.
19. Michaelis, L.; Hill, E. S. J. Gen. Phys. 1933, 16, 859.
20. Schoot, C. J.; Ponjee, J. J.; Van Dam, H. T.; Van Doorn, R. A.; Bolwijn, R. T. Appl. Phys. Lett. 1973, 23, 64.
21. Kuwana, T.; Steckhan, E. Ber. Der. Bunsenges. Phys. Chem. 1974, 78, 253.
22. Monk, P. M. S. The Viologens, John Wiley & Sons, Chichester, UK, 1998, 5.
23. Michaelis, L. Chem. Rev. 1935, 16, 243.
24. Kosower, E.; Cotter, J. I. J. Am. Chem. Soc. 1964, 86, 5524.
25. Kawata, T.; Yamamoto, M. J. Appl. Phys. 1975, 14, 725.
26. Yasuda, A.; Mori, H.; Seto, J. J. Appl. Electrochem. 1987, 17, 567.
27. Monk, P. M. S.; Fairweather, T. D.; Ingram, M. D.; Duffy, J. A. J. Chem. Soc. Perkin Trans.I. 1992, 2, 2039.
28. Hawkridge, F. M.; Stargardt, J. F. Anal. Chim. Acta. 1983, 146, 1.
29. Schwarz, Jr. Ph. D Thesis, University of Wisconsin, Madison, Wisconsin, 1962.
30. Muller, F.; Mayhew, S. G. Biochem. Soc. Trans. 1982, 10, 176.
31. Evens, A. G.; Evens, J. C.; Baker, M. W. J. Chem. Soc., Perkin Trans. II 1977, 1787.
32. Webster, A. G.; Dryfe, R. A. W.; Eklund, J. C.; Lee, C.-W.; Compton, R. G. J. Electroanal. Chem. 1996, 402, 1649.
33. Norton, J. D.; White, H. S. J. Electroanal. Chem. 1992, 325, 341.
34. Mortimer, R. J. Electrochrim. Acta. 1999, 44, 2971.
35. Faughnan, B. W.; Crandall, R. S. “Display Devices”. Sringer-Verlag, Berlin, 1980.
36. Yasuda, A.; Mori, H.; Takehana, Y.; Ohkoshi, A.; Kamiya, N. J. Appl. Electrochem. 1984, 14, 323.
37. Monk, P. M. S. J. Electroanal. Chem. 1997, 432, 175.
38. Shelepin, I. V.; Ushakov, O. A.; Karpova, N. I.; Barachevskii, V. A. Elektrokhimiya. 1977, 13, 32.
39. Shelepin, I. V.; Gavrilov, O. A.; Barachevskii, V. A.; Karpova, N. I. Elektrokhimiya 1977, 13, 404.
40. Shelepin, I. V.; Gavrilov, O. A.; Barachevskii, V. A.; Karpova, N. I. Elektrokhimiya 1978, 14, 319.
41. Shelepin, I. V.; Gavrilov, O. A.; Barachevskii, V. A.; Karpova, N. I. Elektrokhimiya 1985, 21, 918.
42. Leventis, N.; Chung, Y. C. U. S. Patent, 5,457,564 1995.
43. Miles, M. H; Henry, R. A.; Fine, D. A. U. S. Patent, 5516462 1996.
44. Stepp, J.; Schlenoff, J. B. J. Electrochem. Soc. 1997, 144, 1155.
45. Leventis, L.; Chen, M.; Liapis, A. I.; Johnson, J. W.; Jain, A. J. Electrochem. Soc. 1998, 145, 55.
46. Byker, H. J. U. S. Patent, 4,902,108 1990.
47. Yamamoto, T.; Kurata, Y. Can. J. Chem. 1983, 61, 86.
48. Lai, G.; Bu, Xiu R.; Santos, J.; Mintz, Eric A. Synth. Lett. 1997, 11, 1275.
49. Nomura, S.; Nishimura, K.; Shirota, Y. Mol. Cryst. Liq. Cryst. Sci. Technol. Sect. A 1994, 253, 79.
50. Coyle, H.; Marr, E. J.Organomet.Chem. 1973, 60, 153.
51. Kamogawa, H.; Suzuki, T. Bull.Chem.Soc.Jpn. 1987, 60, 794.
52. Kirowa-Eisner, E.; Gileadi, E. J. Electroanal. Chem. 1970, 25, 481.
QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top
系統版面圖檔 系統版面圖檔