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研究生:陳俞臻
研究生(外文):Yu-Jen Chen
論文名稱:自由基對前驅物(氮-苯磺醯取代的吡咯、咪唑及吲哚)的合成與光化學反應
論文名稱(外文):The Synthesis and Photochemistry of Radical Pair Precursors: N-Benzenesulfonyl Substituted Pyrroles, Imidazole and Indole
指導教授:鍾文聖
指導教授(外文):Wen-Sheng Chung
學位類別:碩士
校院名稱:國立交通大學
系所名稱:應用化學系
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:2002
畢業學年度:90
語文別:中文
論文頁數:180
中文關鍵詞:自由基對雙自由基
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一系列含氮-苯磺醯取代的吡咯化合物39、47、52及53在77 K,以MTHF為介質,利用230-325 nm的波長照射測得之EPR光譜,D'值分別為0.0228、0.0225、0.0190及0.0176 cm-1;而47在相同條件下變換低溫介質時,D'值介於0.0219∼0.0225 cm-1之間。在4 K的溫度下,化合物51及47其D'值為0.0239與.0237 cm-1;且分別在12-44 K、與8-52 K的溫度範圍,可得到線性之Curie plot,意即此兩化合物照光所得之自由基對為參重基態,或其單態與參態能階非常接近(ΔES-T ≦30 cal/mole)。由自由基捕捉實驗,亦可單離Ts基與捕捉試劑加成之產物;且具有氮-苯磺醯取代之化合物85、88亦可觀測到EPR之參態自由基訊號,說明氮硫間鍵結極易因照光斷裂,而產生自由基對。因此 Berson教授以化合物18在77 K相同光源及介質下,觀測到的參態自由基其D'值為0.0226 cm-1,此訊號極有可能源自於自由基對而非雙自由基。

A series of 39, 47, 52 and 53 in 2-methyltetrahydrofuran glass matrices at 77 K were irradiated with 230-325 nm (NiSO4-filtered, UV light), which gave triplet EPR spectra, and the zero-field splitting (zfs) parameters D' values are 0.0228, 0.0225, 0.0190 and 0.0176 cm-1, respectively. At 4 K, the D' values of 51 and 47 are 0.0239 and 0.0237 cm-1, respectively. The radical pairs derived from 51 (12-44 K) and 47 (8-52 K) both showed linear Curie plots, thereby indicating either the ground state are triplets or that singlet and triplet states are degenerate (≦30 cal/mole difference). An addition product of Ts and MNP was observed when 51 was photolyzed in the presence of spin trapping agent. N-benzenesulfonyl substituted hetercyclic molecules 85 and 88 also gave triplet EPR spectra, which are consistent with triplet radical pairs. Results indicate that nitro-sulfur bonds were easily cleaved by 230-325 nm photolysis, and the results are supported by ab initio calculations. Therefore, the reported D' value (0.0226 cm-1) of a biradical by Professor Berson in the photolysis of N-tosyl pyrrole diazene 18 (J. A. Berson, J. Am. Chem. Soc. 1997, 119, 1416.) may not be a triplet biradical and could be a triplet radical pair instead.

目錄 頁碼
中文摘要 i
英文摘要 iii
謝誌 v
目錄 vi
式圖目錄 ix
圖目錄 xi
表目錄 xix
附圖目錄 xx
化合物對照表 xxiv
第一章、緒論 1
1-1、研究動機及相關文獻 1
1-2、研究構想 23
第二章、結果與討論 24
2-1、合成部分 24
2-1-1、3,4-Dimethyl-1-[(4-methylphenyl)sulfonyl]-
1H-pyrrole 47的合成 24
2-1-2、1-[(4-Methylphenyl)sulfonyl]-1H-pyrrole
51、52及53的合成 25
2-1-3、α,α´雙硝基取代的N-tosyl-pyrrolosultine
55a, b的合成嘗試 26
2-1-4、2-Pyridine-N-tosyl-pyrrolosultine 62的合成嘗試 28
2-1-5、2,5-Dipyrinide-N-tosyl-pyrrolosultine 66的合成
嘗試 29
2-1-6、p-F-Ph-pyrrolosulotine70的合成嘗試 30
2-1-7、2,4-雙芳基取代N-tosyl-pyrrole 73的合成嘗試 31
2-1-8、2,5-Diphenyl-N-tosyl-pyrrolosultine 79的合成 31
2-2、1-[(4-methylphenyl)sulfonyl]-1H-pyrrole 51的照光反應 35
2-2-1、化合物51單獨照光 35
2-2-2、化合物51與2-methyl-2-nitrosopropane(MNP)
的照光反應 41
2-2-3、化合物51的EPR實驗 44
2-3、1-[(4-methylphenyl)sulfonyl]-1H-imidazole 85
的照光反應 63
2-3-1、1-tosylimidazol化合物85單獨照光 63
2-3-2、1-tosylimidazole化合物85與MNP之照光反應 66
2-3-3、1-tosylimidazol化合物85之EPR實驗 69
2-4、1-(phenylsulfonyl)-1H-indole 88的照光反應 74
2-4-1、1-(phenylsulfonyl)-1H-indole 88照光反應的嘗試 74
2-4-2、1-(phenylsulfonyl)-1H-indole, 化合物88之EPR
實驗 77
第三章、結論 80
第四章、參考文獻 83
第五章、實驗 87
5-1、一般敘述 87
5-2、EPR實驗 89
5-2-1、77K的EPR實驗 89
5-2-2、變溫的EPR 實驗 89
5-3、合成實驗步驟 90
5-4、照光實驗 106
5-4-1、照光實驗步驟 106
5-4-2、照光實驗產物光譜資料 106
附圖 110
附錄 179
簡歷 180

第四章、參考文獻
1. W. T. Borden, H. Iwamura, J. A. Berson, Acc. Chem. Res. 1994, 27, 109.
2. H. C. Longuet-Higgins, J. Chem. Phys. 1950, 18, 265.
3. P. Dowd, J. Am. Chem. Soc. 1966, 88, 2587.
4. P. Dowd, W. Chang, Y. H. Paik, J. Am. Chem. Soc. 1986, 108, 7416.
5. J. A. Berson, Acc. Chem. Res. 1997, 30, 238.
6. (a) K. Matsuda, H. Iwamura, J. Am. Chem. Soc. 1997, 119, 7412. (b) M. Filatov, S. Shaik, J. Phys. Chem. A. 1999, 103, 8885.
7. K. J. Stone, M. M. Greenberg, S. C. Blackstock, J. A. Berson, J. Am. Chem. Soc. 1989, 111, 3659.
8. (a) M. M. Greenberg, S. C. Blackstock, K. J. Stone, J. A. Berson, J. Am. Chem. Soc. 1989, 111, 3671. (b) K. J. Stone, M. M. Greenberg, J. L. Goodman, K. S. Peters, J. A. Berson, J. Am. Chem. Soc. 1986, 108, 8088.
9. (a) M. M. Greenberg, S. C. Blackstock, J. A. Berson, R. A. Merrill, J. C. Duchamp, K. W. Zilm, J. Am. Chem. Soc. 1991, 113, 2318. (b) K. W. Zilm, R. A. Merrill, M. M. Greenberg, J. A. Berson, J. Am. Chem. Soc. 1987, 109, 1567.
10. L. C. Bush, R. B. Heath, X. W. Feng, P. A. Wang, L. Maksimovic, A. I. Song, W. S. Chung, A. B Berinstain, J. C. Scaiano, J. A. Berson, J. Am. Chem. Soc. 1997, 119, 1406.
11. (a) L C. Bush, L. Maksimovic, X. W. Feng, H. S. M. Lu, J. A. Berson, J. Am. Chem. Soc. 1997, 119, 1416. (b) L. C. Bush, R. B. Heath, J. A. Berson, J. Am. Chem. Soc. 1993, 117, 9830.
12. (a) S. M. Helen, J. A. Berson, J. Am. Chem. Soc. 1996, 118, 265. (b) S. M. Helen, J. A. Berson, J. Am. Chem. Soc. 1997, 119, 1428.
13. 吳安台博士論文, 2001年, 國立交通大學
14. 張勇志碩士論文, 2000年, 國立交通大學
15. A. Chakrabarti, G. K. Biswas, D. P. Chakraborty, Tetrahedron 1989, 45, 5059.
16. N. J. Turro,“Modern Molecular Photochemistry”University Science Books: New York, 1991, Chapter 13.
17. T. Drust, J. C. Huang, N. K. Sharma, Can. J. Chem. 1978, 56, 512.
18. (a) P. B. Ayscough, B. R. Brooks, H. E. Evans, J. Phys. Chem. 1964, 68,3889. (b) M. C. R. Symons, Nature. 1967, 231, 1226.
19. (a) C. L. Lau, S. Tardif, C. Dufresne, J. Scheigetz, J. Org. Chem. 1989, 54,491. (b) D. M. Ketcha, K. P. Carpenter, S. T. Atkinson, H. R. Rajagopalan, Synth. Comm. 1990, 20, 1647. (c) Aoi Ono, Nobuko Suzuki, Junko Kamimura, Synthesis. 1987, 736.
20. J. Sisko, M. Mellinger, P. W. Sheldrake, N. H. Baine, Tetrahedron Letters. 1996, 37, 8113.
21. A. R. Katritzky, G. J. Hitchings, X. Zhao, Synthesis, 1991, 863.
22. Shuntaro Matake, K. Takahasi, Y. Tsuda, Synthesis, 1982, 157.
23. M. Baumgarten, N. Tyutyulkov. Chem. Eur. J. 1998, 4, No. 6
24. (a) J. A. Weil,“Electron Paramagnetic Resonance”Wiley: New York, 1994. (b) S. Kinoshi, M. Hoshino, M. Imamura, Chem. Phys. Lett .1981, 82, 217. (c) D. A. Wiersma, J. Kommandeur, Molecular Phys. 1967, 13, 241. (d) V. R. Parish,“NMR, NQR, EPR, and Mossbaure spectroscopy in inorganic chemistry ”Prentice Hall: New York, 1990. Chapter 5.
25. (a) M. Kawano, T. Sano, J. Abe, Y. Ohashi, J. Am. Chem. Soc. 1999, 121, 8106. (b) M. Kawano, T. Sano, J.Abe, Y. Ohashi, Chem. Lett. 2000, 1372. (d) J. Abe, T. Sano, M. Kawano, Y. Ohashi, M. M. Matsushita, T. Iyoda, Angew. Chem. Int. Ed. 2001, 40,580.
26. J. V. Caspar, I. V. Khudyakov, N. J. Turro, Macromolecules, 1995, 28, 636.
27. X. Z. Qin, A. Liu, A. D. Trifunac, J. Phys. Chem. 1991, 95, 5822.
28. M. Somei, M. Natsume, Tetrahedron Lett. 1973, 2451.
29. (a) P. Dowd, W. Chang, Y. H. Paik, J. Am. Chem. Soc. 1987, 109,
5284. (b) W. R. Roth, U. Kowalczik, G. Maier, H. P. Reisenauer, R. Sustmann, W. Müller, Angew. Chem. Int. Ed. Engl. 1987, 26, 1285. (c) M. Rule, A. R. Matlin, D. A. Seeger, E. F. Hilinski, D. A. Dougherty, J. A. Berson, Tetrahedron, 1982, 38, 787. (d) B. L. V. Prased, T. P. J. Radhakrishnan, Mol. Struct. (Theochem) 1996, 361, 175. (e) J. H. Reynolds, J. A. Berson, K. K. Kumashiro, J. C. Duchamp, K. W. Zilm, J. C. Scaiano, A. B. Berinstain, A. Rubello, P. Vogel, J. Am. Chem. Soc. 1993, 115, 8073. (f) L. C. Bush, K. K. Kumashiro, K. W. Zilm, J. A. Berson, unpubished work at Yale University.
30. D. Cichar, M. S. Platz, J. A. Berson, J. Am. Chem. Soc. 1977, 99, 8507.
31. P. Dowd, Acc. Chem. Res. 1972, 5, 242.
32. (a) G. L. Closs, L. R. Kaplan, J. Am. Chem. Soc. 1969, 91, 2168. (b) G. L. Closs, L. R. Kaplan, V. I. Bendall, J. Am. Chem. Soc. 1967, 89, 3376.
33. (a) M. S. Platz, J. M. McBride, R. D. Little, J. J. Harrison, A. Shaw, S. E. Potter, J. A. Berson, J Am. Chem. Soc. 1976, 98, 5725. (b) R. J. Baseman, D. W. Pratt, M. Chown, P. Dowd, ibid 1976, 98, 6726.
34. (a) S. L. Buchwalter, G. L. Closs, J Am. Chem. Soc. 1975, 97, 3857. (b) M. S. Platz, J. A. Berson, J Am. Chem. Soc. 1976, 98, 6743. (c) P. Dowd, M. Chow, J Am. Chem. Soc. 1977, 99, 6538.
35. T. D. Duffy, D. G. Wibberley, J. Chem. Soc. Perkin Trans I, 1974, 1921
36. (a) R. Breslow, H. W. Chang, R. Hill, E. Wasserman, J Am. Chem. Soc. 1967, 89, 1112. (b) M. Minato, P. M. Lahti, J Am. Chem. Soc. 1997, 119, 2187.

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