臺灣博碩士論文加值系統

Calixarenes，為一種酚和甲醛的環狀聚合物，因為其具有分子內中空，故可以嵌合一些小型的有機分子或金屬離子，而形成 “主-客化合物”，而這一種特性應可推廣應用於微量檢驗，離子分離及酵素模擬的研究；而本論文主要的目的首先是合成出一系列 1,3-雙烷基醚化的 calix[4]arenes，接著利用 ClO2 的氧化能力，來製備出一系列 1,3-雙烷基醚化的 calix[4]diquinones；本論文進一步的進行雙乙基醚化之氧化的動力學研究，並期望藉由雙乙基醚化之calix[4]arenes 進行苯甲酸單一酯化，再進行氧化的實驗，最終水解；藉由此最終產物與1-3 diethoxycalix[4]diquinones的差異進行比較。
p-tert-Butylphenol 和甲醛在鹼催化下可聚合成黃綠色之聚合前驅物 26，此一聚合前驅物於二苯醚 (diphenyl ether) 中迴流可被轉換成 p-tert-butylcalix[4]arene (1)；而此環狀聚合物上的對位三級丁基可再利用三氯化鋁 (AlCl3) 作為催化劑，以反向的 Friedel-Crafts 反應移除，而得到對位無取代之 calix[4]arene (6)。
依據文獻報導，calix[4]arene 和多量的鹵化烷類及 K2CO3 在 CH3CN 中迴流，可得到高產率的 1,3-雙烷基醚化之 calix[4]arenes；而本論文則採用了碘化乙烷 (iodoethane)，碘化正丙烷 (1-iodopropane)，碘化正丁烷 (1-iodobutane)，溴化甲苯 (benzyl bromide)，和溴化丙烯 (allyl bromide) 等五種鹵化烷類，來製備出相
對應的 25,27-diethoxy-26,28-dihydroxycalix[4]arene (27)、25,27-di-
propoxy-26,28-dihydroxycalix[4]arene (28)、25,27-dibutoxy-26,28-di-
hydroxycalix[4]arene (29)、25,27-dibenzyloxy-26,28-dihydroxycalix[4]-
arene (30) 及 25,27-diallyloxy-26,28-dihydroxycalix[4]arene (31)。
本實驗室曾成功的利用 ClO2 將雙烷基醚化的 calix[4]arenes 氧化成為相對應的 calix[4]quinones，本論文亦利用相同的 ClO2 氧化特性，來對雙烷基醚化之 calix[4]arenes 進行氧化。其中發現乙基醚的官能團能經由亞甲基之單鍵向環內作翻轉，而得到syn-25,27-diethoxy-26,28-calix[4]diquinone (32) 和anti-25,27-diethoxy-
26,28-calix[4]diquinone (33) 之外，其餘的氧化反應均只能得到其相對應之 25,27-dipropoxy-26,28-calix[4]diquinone (34)、25,27-dibutoxy-
26,28-calix[4]diquinone (35)、25,27-dibenzyloxy-26,28-calix[4]di-
quinone (36) 及 25,27-diallyloxy-26,28-calix[4]diquinone (37)。
因此本論文將探討雙乙基醚化之calix[4]diquinones的動力學研究，利用1HNMR的光譜測量來計算syn組態與anti組態的百分比，並利用動力學一級反應的公式 (a0/xe)ln(xe/xe-x)=k1t 計算出在CDCl3與C5D5N的 K1值

Calixarenes, which are cyclic oligomers of p-substituted phenols and formaldehyde, are able to include small organic molecules or metal ions within the molecular cavities to form ‘‘ host-guest ’’ complexes. These phenomena have been proposed in the applications of micro-analysis, ion separation, and enzyme-mimic studies. The main purpose of this thesis is to synthsis 1,3-diethoxycalix[4]diquinones and study its kinetic。
p-tert-Butylphenol and formaldehyde was polymerized, in the presence of a base, to form an yellowish precursor 26. Refluxing of this precursor in diphenyl ether yielded the p-tert-butylcalix[4]arene (1). The p-tert-butyl groups were then removed with AlCl3 by reverse Friedel-Crafts reaction to give the parent calix[4]arene (6).
Literature reported that calix[4]arene was dialkylated by refluxing with alkyl halides and potassium carbonate in acetonitrile for 4 hours. Five alkyl halides (iodoethane, 1-iodopropane, 1-iodobutane, benzyl bromide, and allyl bromide) were selected in this thesis, and the corresponding syn-1,3-dialkoxycalix[4]arenes 27, 28, 29, 30 and 31 were prepared.
The chlorine dioxide oxidation was performed on these 1,3-dialkylated calix[4]arenes, and except for the case of diethoxy-
calix[4]arene, which afforded syn- and anti- stereoisomers of diethoxy-
calix[4]diquinones 32 and 33, the other dialkoxycalix[4]arenes yielded the corresponding calix[4]diquinones 34, 35, 36 and 37.
The main purpose of this thesis is to study the kinetic of 1,3-diethoxycalix[4]diquinones and use 1H-NMR to calculate proportion of syn-32 and anti-33，and used first order of kinetic formula to calculate
K1。
All of the products were characterized by 1H-NMR, 13C-NMR, COSY, FAB-MS, and EA.

目 錄

頁 碼
摘 要 .................................................................................................... I

Abstract ....................................................................................................... IV

目 錄 ....................................................................................................VI

圖 目 錄 ....................................................................................................IX

流程目錄 ....................................................................................................XI

表 目 錄 ................................................................................................... XIII

第一章 Calixarenes 的簡介
1-1 Calixarenes 的歷史 ………………………………………….. 1
1-2 Calixarenes 的命名 ………………………………………….. 3
第二章 Calixarenes 的應用
2-1 Calixarenes 的組構異構物 …………………….…….…….… 6
2-2 Calixarenes 的應用 …………….…………………………… 11
第三章 Calixarenes 的合成
3-1 一步合成法 ………………………………………………..… 27
3-2 多步合成法 ………………………………………………….. 29
3-3 官能基化法 ………………………………………………….. 34
第四章 雙烷基醚化 Calix[4]diquinones 的合成
4-1 Calix[4]arenes 的製備 …………………………………….... 42
4-2 1,3-Dialkyloxycalix[4]arenes 的合成 ………………………. 42
4-3 1,3-Dialkyloxycalix[4]arenes 的 1H-NMR 光譜
的光譜分析.…………………………………………………... 43
4-4 1,3-Dialkoxycalix[4]diquinone 的合成………………………. 44
4-5 1,3-Dialkoxycalix[4]diquinones 的 1H-NMR 光譜分析...….. 46
4-6 雙乙基醚化之 calix[4]arenes 的酯化合成……………………47
4-7 雙乙基醚化之 calix[4]arenes 的酯化的氧化合成……………49


第五章 對位乙醯雙取代之 calix[4]arene 的合成研究
5-1 1,3-Diethyloxycalix[4]diquinone 的動力研究……................. 50
5-2 First Order動力學公式的推導…………………………………51
5-3 syn-1,3-Diethyloxycalix[4]diquinone (32) in CDCl3的測量
………………………………………………................................51
5-4 anti-1,3-Diethyloxycalix[4]diquinone (33) in CDCl3的測量…………………………………………………………………55
5-5 syn-1,3-Diethoxycalix[4]diquinone (32) in C5D5N的測量…………………………………………………………………58
5-6 anti-1,3-Diethoxycalix[4]diquinone (32) in C5D5N的測量…………………………………………………………………61


結 論 ……………………………………………………………….... 63

實驗步驟 …………………………………..……………………….……..65

參考資料 ……………………………….………………………...……….78

光 譜 圖………………………………………………….…….………….85

參 考 資 料


1.Baeyer, A. Ber. Dtsch. Chem. Ges., 1872, 280.

2.Baekeland, L. H. Indust. Eng. Chem., 1913, 5, 506.

3.Zinke, A.; Kretz, R.; Leggewie, E.; Hossinger, K. Monatsh. Chem., 1952, 83, 1213

4.Cornforth, J. W.; Hart, P. D.; Nicholls, G. A.; Rees, R. J. W.; Stock, J. A. Brit. J. Pharmacol., 1955, 10, 73.

5.Kammerer, H.; Happel, G.; Caesar, F. Makromol. Chem., 1972, 162, 179.

6.Munch, J. H. Makromol. Chem., 1977, 178, 69.

7.Gutsche, C. D.; Muthukrishnan, R. J. Org. Chem., 1978, 43, 4905.

8.Andreetti, G. D.; Ungaro, R.; Pochini, A. J. Chem. Soc. Chem. Commun., 1979, 1005.

9.Shinkai, S.; Mori, S.; Tsubaki, T.; Sone, T.; Manabe, O. Tetrahedron Lett., 1984, 25, 5315.

10.Helgeson, R. C.; Mazaleyrat, J. P.; Cram, D. J. J. Am. Chem. Soc., 1981, 103, 3929. (b) Moran, J. R.; Karbach, S.; Cram, D. J. J. Am. Chem. Soc., 1982, 104, 5826. (c) Cram, D. J. Science, 1983, 219, 1177.

11.Gutsche, C. D.; Dhawan, B.; Levine, J. A.; No, K. H.; Bauer, L,. J Tetrahedron, 1983, 39, 409.

12.Bocchi, V.; Foina, D.; Pochini, A.; Ungaro, R. Tetrahedron, 1982, 38, 373.

13.Cram D. J.; Cram, J. M. Science., 1974, 183, 803.

14.Bauer, L. J.; Gutsche, C. D. J. Am. Chem. Soc., 1987, 107, 6063.

15.Shinkai, S. J. Incl. Phenom., 1989, 7, 193.

16.Gutsche, C. D.; Alam, I.; Iqbal, M.; Mangiafico, T.; Nam, K. C.; Rogers, J.; See, K. A. J. Incl. Phenom., 1989, 7, 61.

17.Molenveld, P.; Emgbersen, J. F. C.; Kooijman, H.; Spek, A. L.; Reinhoudt, D. N. J. Am. Chem. Soc., 1998, 120, 6726.

18.Gutsche, C. D.,Am. Chem. Soc.,1983,16,161.

19.Izatt, R. M.; Lamb, J. D.; Hawkins, R. T.; Brown, P. R.; Izatt, S. R.; Christensen, J. J. J. Am. Chem. Soc., 1983, 105, 1782.

20.Zhen-lin Zhong; Yuan-yin Chen; Xue-ran Lu Tetrahedron Lett., 1995, 36, 6735.

21.Benco, J. S.; Nienaber, H. A.; Dennen, K.; McGimpsey, W. G. Journal of Photochemistry and Photobiology A：Chemistry, 2002, 152, 33.

22.(a) Shinkai, S.; Koreishi, H.; Ueda, K.; Manabe, O. J. Chem. Soc. Chem. Commun., 1986, 233. (b) Shinkai, S.; Koreishi, H.; Ueda, K.; Arimura, T.; Manabe, O. J. Am. Chem. Soc., 1987, 109, 6371. (c) Shinkai, S.; Kawaguchi, H.; Manabe, O. J. Polym. Sci. Polym. Lett., 1988, 26, 391. (d) Shinkai, S.; Shiramama, Y.; Satoh, H.; Manabe, O. J. Chem. Soc. Perkin Trans. 2, 1989, 1167.

23.Wanlapa, A.; Agnes, H.; Zouhair, A.; Leila B.; Jacques, V.; Maurice, L. Tetrahedron Lett., 1999, 40, 6389.

24.Rocco Ungaro; Alessandro Casnati; Franco Ugozzol; Andrea Pochini; Jean-Francois Dozol; Clement Hill; Helene Rouquette Angew Chem Int Engl, 1994, 32,1506.

25.Duncan, D. M.; Cockayne, J. S. Sensors and Actuators B, 2001, 73, 228.

26.Jain, V. K.; Handa, A.; Pandya, R.; Shrivastav, P.; Agrawal, Y.K. Reactive ＆ Functional Polymers, 2002, 51, 101.

27.Nomura, E.; Taniguchi, H.; Tamura, S. Chem. Lett., 1989, 1125.

28.Shimizu, H.; Iwamoto, K; Fujimoto, K; Shinkai, S. Chem. Lett, 1991,2147.

29.Kim, N. Y.; Chang, S.-K. J. Org. Chem, 1998, 63, 2362.

30.Tao Zhao, X. Hu, J. Cheng, X. Lu Analytica Chimica Acta, 1998, 358, 263.

31.(a) Zinke, A.; Ziegler, E. Ber. Chem., 1941, 74, 1729. (b) Zinke, A.; Ziegler, E. Ber. Chem., 1944, 77B, 264. (c) Zinke, A.; Zigeuner, G.; Hossinger, K.; Hoffman, G. Monatsh. Chem., 1948, 79, 438. (d) Zinke, A.; Ott, R.; Garrana, H. Monatsh. Chem., 1958, 89, 135. (e) Zinke, A. J. Appli. Chem., 1951, 1, 135.

32.Patrick, T. B.; Egan, P.A. J. Org. Chem., 1977, 42, 382.

33.Gutsche, C. D.; Dhawan, B.; No, K. H.; Muthukrishnan, R. J. Am. Chem. Soc., 1981, 103, 3782.

34.Gutsche, C. D.; Iqbal, M. Org. Synth., 1989, 68, 234.

35.Ninagawa, A.; Matsuda, H. Makromol. Chem. Rapid Comm., 1982, 3, 65.

36.Nakamoto, Y.; Ishida, S. Makromol. Chem. Rapid Comm., 1982, 3, 705.

37.(a) Hayes, B. T.; Hunter, R. F. Chem. Ind., 1956, 193. (b) Hayes, B. T.; Hunter, R. F. J. Applied Chem., 1958, 8, 743.

38.(a) Happel, G.; Mathiasch, B.; Kammerer, H. Makromol. Chem., 1975, 176, 3317. (b) Kammerer, H.; Happel, G. Makromol. Chem., 1978, 179, 1199. (c) Kammerer, H. Monatsh. Chem., 1981, 112, 759.

39.Bohmer, V.; Chhim, P.; Kammerer, H. Makromol. Chem., 1979, 180, 2503.
40.(a) Hakimelahi, G. H.; Moshfegh, A. A. Helv. Chim. Acta, 1981, 64, 599. (b) Moshfegh, A. A.; Mazandarani, B.; Nahid, A.; Hakimelahi, G. H. Helv. Chim. Acta, 1982, 65, 1229. (c) Moshfegh, A. A.; Baladi, E.; Radnia, L.; Afsanch, S. L.; Hosseini, A. S.; Tofigh, S.; Hakimelahi, G. H. Helv. Chim. Acta, 1982, 65, 1264.

41.No, K. H.; Gutsche, C. D. J. Org. Chem., 1982, 47, 2713.

42.Gutsche, C. D.; Alam, I. Tetrahedron, 1988, 44, 4689.

43.Gutsche, C. D.; Levine, J. A. J. Am. Chem. Soc., 1982, 104, 2652.

44.Bohmer, V.; Rathay, D.; Kammerer, H. Org. Prep. Proc. Int., 1978, 10, 113.

45.(a) Shinkai, S.; Tsubaki, T.; Sone, T.; Manabe, O. Tetrahedron Lett., 1985, 26, 3343. (b) Shinkai, S.; Araki, K.; Tsubaki, T.; Arimur, T.; Manabe, O. J. Chem. Soc. Perkin Trans. 1, 1987, 2297. (c) Arimur, T.; Shinkai, S.; Matsuda, T.; Hirata, Y.; Satoh, H.; Manabe, O. Bull. Chem. Soc. Jpn., 1988, 61, 3733. (d) Shinkai, S.; Arimura, T.; Araki, K.; Kawabata, H. J. Chem. Soc. Perkin Trans. 1, 1989, 2039. (e) Arimura, T.; Nagasaki, T.; Shinkai, S.; Matsuda, T. J. Org. Chem., 1989, 54, 3766.

46.Rosik, L. O., Ph. D. Thesis, Washington University, St. Louis, 1986, p 29.

47.Gutsche, C. D.; Reddy, P. A. J. Org. Chem., 1993, 58, 3245.

48.Ming-Dar Lee, Ker-Ming Yang, Ching-Yu Tsoo, Chun-Mei Shu, Lee-Gin Lin Tetrahedorn, 2001, 57, 8095.

49.Ker-Ming Yang, Ming-Dar Lee, Rong-Fua Chen, Yi-Lin Chen,
Lee-Gin Lin Tetrahedron, 2001, 57, 8101.

50.Reinhoudt, D.N.; Groenen, L.C.; Ruel, B.M.; Casnati, A.; Timmerman, P.; Verboom, W.; Pochinin, A.; Ungaro, R. Tetrahedron Lett., 1991, 32, P.; Verboom, W.; Pochinin, A.; Ungaro, R. Tetrahedron Lett., 1991, 32, 2675.
51.Iwamoto, K.; Araki, K.; Shinkai, S. J. Org. Chem. 1991, 56, 4956.

52.Tzer-Shun, Yu, M. S. D. Thesis, Chinese Culture University, Taiwan, Taipei, 2003, 45.

53. Gutsche, C. D.; Pagoria, P. F., J. Org. Chem., 1985, 50, 5795.