簡易檢索 / 詳目顯示
| 研究生： |
莊博能 Po-Neng Chuang |
|---|---|
| 論文名稱： |
六氟化磷陰離子協助下甲基苯基酮衍生物之醛醇環三聚合反應研究 Hexafluorophosphate Anion Assisted Aldol Cyclotrimerization of Acetophenone Derivatives |
| 指導教授： |
劉陵崗
Ling-Kang Liu |
| 口試委員: | |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學學系 Department of Chemistry |
| 畢業學年度： | 95 |
| 語文別： | 中文 |
| 論文頁數： | 98 |
| 中文關鍵詞： | 醛醇反應 、六氟化磷陰離子 、離子液體 |
| 外文關鍵詞： | Hexafluorophosphate Anion, aldol reaction, ionic liquid |
| 相關次數： | 點閱：17 下載：0 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
在甲基芳香基酮衍生物(A1-D1)存在下，離子液體bmimPF6與相關含PF6-陰離子的鹽類，長時間維持在>90℃，PF6-陰離子會解離出氟陰離子及強路易士酸PF5，進而催化A1-D1的醛醇反應，產生雙聚體(A2-D2)、成環三聚體(A3-D3)與氧鎓鹽化合物(A4-D4)，其中芳香基為苯基(A)、p-甲苯基(B)、p-甲氧基苯基(C)、p-溴苯基(D)。苯環上不同取代基的電子效應會影響到產物的產率比。
A3-D3為1,3,5-三芳香基苯，中間之苯環上的質子受到外圍苯環環電流影響，總感應磁場增加，使得去遮蔽效應增大，故1H-NMR光譜中間苯環質子的吸收訊號會較外圍苯環質子的吸收訊號低場；A4-D4為2,4,6-三芳香基氧鎓鹽，因含有帶正電荷的氧鎓鹽使得去遮蔽效應更大，故氧鎓環上質子的吸收峰訊號位置在更低場的地方。對於氧鎓鹽A4、B4與C4的13C-NMR光譜碳的吸收訊號而言，如果外圍苯環對位碳所接的取代基推電子性質愈強，則外圍苯環碳的化學位移會往低場偏移，而氧鎓環電子密度增加，其上碳的吸收峰訊號會往高場偏移；相同的，外圍苯環上取代基推電子性質愈強，氧鎓鹽的還原半電位愈高、吸收放射峰愈往紅移且量子產率愈大。
In this study, we demonstrated the reaction between ionic liquid bmimPF6 and acetophenone derivatives. Upon heating constantly, the PF6- anion of bmimPF6 decomposes to fluoride anion and PF5. The strong Lewis acid PF5 then activates acetophenone derivatives easily to proceed with the aldol condensation to yield dimer(A2-D2), cyclic trimer(A3-D3) and strongly fluorescent pyrilium salt(A4-D4). The more electron-releasing substituent on aryl ring of acetophenone produces more pyrilium salt.
The structure of A3-D3, a 1,3,5-triarylbenzene, allows the ring current on the peripheral phenyl rings to affect de-shielding by the inner phenyl ring protons. Hence, the chemical shifts of inner phenyl protons are down-field to those of peripheral phenyl protons. The chemical shifts of protons on 2,4,6-triarylpyrylium core (A4-D4) are further down-field, attributed to the positive charge of pyrylium ring. For the series of A4, B4, and C4, the electron-releasing substituent on peripheral phenyl ring also leads to the down-field shift on the 13C signals of phenyl ring, whereas, with the increase of electron density on the pyrylium ring, the 13C chemical shifts move up-field. Moreover, the stronger electron-releasing substituent on peripheral phenyl ring, the higher red-shift for UV-visible and PL spectra, with also greater quantum yield.
1、Wouter, V.; Mark, V. D. A.; Frans, C. D. S.; Jacob, J. P.; John, M. W. J. Am. Chem. Soc. 1998, 120, 1319.
2、Ponomarenko, S. A.; Kirchmeyer, S.; Elschner, A.; Huisman, B.-H.; Karbach, A.; Drechsler, D. Adv. Funct. Mater. 2003, 13, 591.
3、Blanchard-Desce, M. Chem. Mater. 2003, 15, 4139.
4、(a) Liu, L.; Zhang, Y.; Xin, B. J. Org. Chem. 2006, 71, 3994. (b) Pena, M. A.; Sestelo, J. P.; Sarandeses, L. A. Synthesis 2005, 485.
5、Cadierno, V.; Garcia-Garrido, S. E.; Gimeno, J. J. Am. Chem. Soc.2006, 128, 15094.
6、Lyle, R. E.; DeWitt, E. J.; Nichols, N. M.; Cleland W. J. Am. Chem. Soc. 1953,75, 5959.
7、Hoff, H.; Schweizer, H. R.; Ghertsos, A.; Heer, A.; Solarsky, A. Chimia 1958, 12, 143.
8、Fujii, R. J. Chem. Soc. Japan, Pure Chem. Sert. 1948, 69, 151.
9、Basting, D.; Schaefer, F. P.; Steyer, B. New J. Chem. 1974, 14, 81.
10、Corma, A.; Fornes, V.; Garcia, H.; Miranda, M. A.; Primo, J.; Sabater, M. J. J. Am. Chem. Soc. 1994, 116, 2276.
11、Miranda, M. A.; Garcia, H. Chem. Rev. 1994, 94, 1063.
12、Wu, S. K.; Chen, Y.; Wang, P. F. J. Lum. 1995, 65, 257.
13、 Dilthey, W. J. Prakt. Chem. 1916, 94, 53.
14、（a）Dorofeenko, G. N.; Krivun, S. V. Zh. Obshch. Khim. 1964, 34, 105. （b）Dinculescu, A.; Bablaban, A. T. Org. Prep. Proced. Int. 1984, 16, 407.
15、（a）Lombard, R.; Stephan, J. P. Bull. Soc. Chim. Fr. 1958, 1458. （b）Dimroth, K.; Berndt, A.; Reichardt, C. Org. Synth. Coll. Vol. V 1973, 1128.
16、http://en.wikipedia.org/wiki/Aldol_reaction
17、Boorum, M. M.; Vasil’ev, Y. V.; Drewello, T.; Scott, L. T. Science 2001,294, 828.
18、Boorum, M. M.; Scott, L. T. In Modern Arene Chemistry; Astruc, D., Ed.;Wiley: New York, 2002; Chapter 1.
19、Sampey, J. R. J. Am. Chem. Soc. 1940, 62, 1953.
20、Calloway, N. O.; Green, L. D. J. Am. Chem. Soc. 1937, 59, 809.
21、Mahmoodi, N. O.; Hajati, N. J. Chin. Chem. Soc. 2002, 49, 91.
22、Hariharan, K. V.; Sudborough, J. J. J. Indian Inst. Sci. 1925, 8A, 189.
23、（a）Elmorsy, S. S.; Pelter, A.; Smith, K. Tetrahedron Lett. 1991, 32, 4175. （b）Praveen, K. T.; KaKali, C.; Carrell, H. L.; Sambasivarao, K.; Gautam, R. D. Tetrahedron 2000, 56, 6721.
24、Li, Z.; Sun, W.-H.; Jin, X.; Shao, C. Synlett 2001, 1947.
25、Iranpoor, N.; Zeynizaded, B. Synlett. 1998, 1079.
26、Bello, A. M.; Kotra, L. Tetrahedron Lett. 2003, 44, 9271.
27、Elderfield, R. C.; King, T. P. J. Am. Chem. Soc. 1954, 76, 5437.
28、Manuel, S.; Eloy, V.-L.; Marina, V.; Lorena, B.; Jorge, C.; Rosario, R.-G. J. Mex. Chem. Soc. 2006, 50, 114.
29、Carmichael, A. J.; Earle, M. J.; Holbrey, J. D.; Mccormac, P. B.; Seddon, K. R. Org. Lett. 1999, 1, 997. 30、Mathews, C. J.; Smith, P. J.; Welton, T. Chem. Commun. 2000, 1249.
31、Pan, X.; She, X.; Li, Y.; Zhang, J.; Wang, W.; Miao, Q. J. Org. Chem. 2005, 70,3285.
32、Lee, C. W. Tetrahedron Lett. 1999, 40, 2461.
33、Xiao,J.-L.; Xu, L.-J.; Mo, J. J. Am. Chem. Soc. 2005, 127, 751.
34、Wang, J.; Niu, H.; Zhang, X. J. Chem. Res. 2003, 33.
35、（a）Cordova, A. Tetrahedron Lett. 2004, 45, 3949. （b）Loh, T.-P.; Feng, L.-C.; Yang, H.-Y.; Yang, J.-Y. Tetrahedron Lett. 2002, 43, 8741.
36、Xu, K. Chem. Rev. 2004, 104, 4303.
37、Hatanaka, K.; Kasuya, M. C. Macromolecules 1999, 32, 2131.
38、Ames, D. P.; Ohashi, S.; Callis, C. F.; Wazer, J. R. J. Am. Chem. Soc. 1959, 81,6350.
39、Saeva, F. D.; Oli, G. R. J. Am. Chem. Soc. 1980, 120, 299.
40、Huddleston, J. G.; Visser, A. E.; Reichert, W. M.; Willauer, H. D.; Broker, G. A.; Rogers, R. D. Green Chem. 2001, 3, 156.
41、Kosmulski, M.; Gustafsson, J.; Rosenholm, J. B. Thermochim. Acta 2004, 412, 47.
42、Hu, Z. G.; Liu, J.; Li, G.A.; Dong, Z. B. J. Chem. Res. 2003, 778.
