(3.237.234.213) 您好!臺灣時間:2021/03/09 12:22
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:莊敬
研究生(外文):Gary Jing Chuang
論文名稱:芳香雜環駢苯駢於Di-π-methane反應中之取代基效應
論文名稱(外文):Substituent Effect on Di-π-Methane Reaction of Benzopyrazinobarrelene and Benzoquinoxalinobarrelene
指導教授:廖俊臣
指導教授(外文):Chun-Chen Liao
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:2007
畢業學年度:96
語文別:英文
論文頁數:156
中文關鍵詞:蓓菉苓取代基效應光重排反應雙自由基中間體
相關次數:
  • 被引用被引用:0
  • 點閱點閱:138
  • 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
本研究主題為利用苯基雜芳香環蓓菉苓(桶狀烯)作為研究模型,用以探討取代基效應對於此類化合物在di-π-methane(DPM)重排反應時的影響。本實驗在設計上借鑑以往之相類似研究所得之成果,利用雜芳香環之取代基的影響,使目標反應之化學選擇性(chemoselectivity)限制於雜環-烯基(pyrazino-vinyl)橋聯之單一反應途徑,故可使反應單純化,以便於探討其取代基效應在此光重排反應中位向選擇性(regioselectivity)的引導作用。文中除了以DPM反應中特有的雙自由基中間體(biradical intermediate)的相對穩定性作為反應途徑探論之基礎,同時亦佐理論計算以求對實驗結果作完善合理的解釋。
The target research is regard of utilizing benzopyrazinobarrelene (BPB) and benzoquinoxalinobarrelene (BQB) as experimental platforms to examine the substituent effect on the di-π-methane (DPM) rearrangement of barrelene-like skeleton. By selecting the appropriate functionality on the pyrazine ring (in this case, the di-cyano groups or an extra benzene ring), the photoreaction could be limited into chemoselectivity of aza-di-π-methane reaction only, thus facilitate the examination of regioselectivity induced by installations of substituents on the bicyclo[2.2.2] skeleton of substrates. The result of the photoreaction was then given rationale by the relative stability of intermediate (biradical) along with theoretical calculation.
TABLE OF CONTENTS
Page

ACKNOWLEDGEMENTS i
ABSTRACT OF THE DISSERTATION v
ABSTRACT OF THE DISSERTATION (in Chinese) vi
ABBREVIATIONS vii
LIST OF CHARTS viii
LIST OF TABLES ix

Chapter I. Introduction and Research Motive
I-1. Di-π-Methane Rearrangement -1-
I-2. Chemistry of Masked-o-Benzoquinones -5-
I-3. Research on Photochemistry of Benzopyrazinobarrelenes -7-
I-4. Purpose and Research Proposal of the Current Study -10-

Chapter II. Synthesis of Benzopyrazinobarrelenes and Benzoquinoxalinobarrelenes
II-1. The Synthesis of Benzobicyclo[2.2.2]octenones -15-
II-2. The Synthesis of Benzobicyclo[2.2.2]octendiones -25-
II-3. Condensation of Benzobicyclo[2.2.2]octendiones to 1,2-Diamines -30-

Chapter III. Photolysis of Benzopyrazinobarrelenes and Benzoquinoxalinobarrelenes
III-1. General Reaction Condition and Procedure -40-
III-2. Result and Analysis
III-2-1. Starting Model Compound -43-
III-2-2. Group I: Steric Effect Target Compounds
III-2-2-1. Group I-1: Alkyl Substitutions on the Olefin. -48-
III-2-2-2. Group I-2: Alkyl Substitutions on Bridgehead Position
-50-
III-2-2-3. Group I-3: Alkyl Substitutions on Both Bridgehead Position and Olefin -54-
III-2-3. Group II: Electronic Effect Target Compounds
III-2-3-1. Group II-1: Functional Groups on the Olefin -57-
III-2-3-2. Group II-2: Functional Groups on the Bridgehead -61-
III-3. Result Summary -65-

Chapter IV. Discussion and Theoretical Calculation
IV-1. Results Concluded in Reported Literatures of Past Research -66-
IV-2. Regioselectivity Ratio Obtained From This Study -70-
IV-3. Prediction of Biradical Intermediate’s (BR-1) Stability by Theoretical Calculation -73-

Chapter V. Conclusions -79-
General Experimental Details -84-

Spectral Data Section -102-

References and Notes -153-

Appendix A-0
(1) Zimmerman, H. E.; Grunewald, G. L. J. Am. Chem. Soc. 1966, 88, 183.

(2) (a) Zimmerman, H. E.; Cirkva, V. Org. Lett. 2000, 2, 2365. (b) Zimmerman, H. E.; Armesto, D. Chem. Rev. 1996, 96, 3065. (c) Armesto, D. In Handbook of Photochemistry and Photobiology, (Eds.: Horspool, W. M.; Song, P.-S.), CRC Press: Florida, 1995, Chapter 73. (d) Zimmerman, H. E. Org. Photochem. 1991, 11, 1. (e) Zimmerman, H. E. In Rearrangements in Ground and Excited States, (Ed.: de Mayo, P.), Academic Press: New York, 1980, Vol. 3, 131. (f) Hixson, S. S.; Mariano, P. S.; Zimmerman, H. E. Chem. Rev. 1973, 73, 531.

(3) (a) Zimmerman, H. E.; Binkley, R. W.; Givens, R. S.; Grunewald, G. L.; Sherwin, M. A. J. Am. Chem. Soc. 1969, 91, 3316. (b) Zimmerman, H. E.; Binkley, R. W.; Givens, R. S.; Sherwin, M. A. J. Am. Chem. Soc. 1967, 89, 3932.

(4) (a) Adam, W.; Lucchi, O. D.; Dorr, M. J. Am. Chem. Soc. 1989, 111, 5209. (b) Adam, W.; Don, M.; Kron, J.; Rosenthal, R J. J. Am. Chem. Soc. 1987, 109, 7074. (c) Reguero, M.; Bernardi, F.; Jones, H.; Olivucci, M.; Ragazos, I. N.; Robb, M. A. J. Am. Chem. Soc. 1993, 115, 2073. (d) Paquette, L. A.; Varadarajan, A.; Burke, L. D. J. Am. Chem. Soc. 1986, 108, 8032. (e) Paquette, L. A.; Bay, E. J. Org. Chem. 1982, 47, 4597. (f) Adam, W.; Carballeira, R. N.; Lucchi, O. D. J. Am. Chem. Soc. 1980, 102, 2107.

(5) (a) Zimmerman, H. E.; Paufler, R. M. J. Am. Chem. Soc. 1960, 82, 1514. (b) Zimmerman, H. E.; Grunewald, G. L.; Paufler, R. M.; Sherwin, M. A. J. Am. Chem. Soc. 1969. 91, 2330.

(6) (a) Zimmerman, H. E.; Grunewald, G. L. J. Am. Chem. Soc. 1966, 88, 183. (b) Zimmerman, H. E.; Binkley, R. W.; Givens, R. S.; Sherwin, M. A. J. Am. Chem. Soc. 1967, 89, 3932.

(7) Houk, K. N. Chem. Rev. 1976, 76, 1.

(8) (a) Liao, C.-C.; Peddinti, R. K. Acc. Chem. Res. 2002. 35, 856. (b) Liao, C.-C.; Chu, C.-S.; Lee, T.-H.; Rao, P. D.; Ko, S.; Song, L.-D.; Shiao. H.-C. J. Org. Chem. 1999, 64, 4102. (c) Liao, C.-C. Pure Appl. Chem. 2005. 77, 1221. (d) Berney, D.; Deslongchamps, P. Can. J. Chem. 1969, 47, 515. (e) Deslongchamps, P.; Berlanger, A.; Berney, D. J. F.; Borschberg, H. J.; Brousseau, R.; Doutheau, A.; Durand, R.; Katayama, H.; Lapalme, R.; Leturc, D. M.; Liao, C.-C.; Maclachlan, F. N.; Maffrand, J.-P.; Marazza, F.; Martino, R.; Moreau, C.; Ruest, L.; Saint-Laurent, L.; Saintonge, R.; Soucy, P. Can. J. Chem. 1990, 68, 115. (f) Hsu, D.-S.; Rao, P. D.; Liao, C.-C. Chem. Commun. 1998, 1795. (g) Hsu, P.-Y.; Lee, Y.-C.; Liao, C.-C. Tetrahedron Lett. 1998, 39, 659. (h) Lee, T.-H.; Liao, C.-C.; Liu, W.-C. Tetrahedron Lett. 1996, 37, 5897. (i) Hsu, D.-Y.; Liao, C.-C. Org. Lett. 2003, 5, 4741. (j) Yen, C.-F.; Liao, C.-C. Angew. Chem., Int. Ed. 2002, 41, 409. (k) Chou, Y.-Y. 2002, Master degree thesis. Department of Chemistry, National Tsing-Hua University, Taiwan. (l) Chou, Y.-Y.; Peddinti, R. K.; Liao, C.-C. Org. Lett. 2003, 5, 1637. (m) Chang, C.-P. 2007, Ph. D. thesis. Department of Chemistry, National Tsing-Hua University, Taiwan. (n) Lin, K.-C.; Yang, C.-S.; Lu, P.-H.; Ph. D. thesis. Department of Chemistry, National Tsing-Hua University, Taiwan.

(9) (a) Chen, C.-P.; Liao, C.-C.; Lin, H.-S. Proc. Natl. Sci. Counc. B. ROC. 1982, 6, 422. (b) Chen, C.-P.; Liao, C.-C.; Lin, H.-S.; Tang, C.-P.; Wang, J.-L.; Hseu, T.-H. Proc. Natl. Sci. Counc. B. ROC. 1983, 7, 246. (c) Ueng, Y.-G.; Liao, C.-C. Tetrahedron Lett. 1990, 31, 1563. (d) Liao, C.-C.; Hseu, T.-H.; Lin, H.-S.; Tang, C.-P.; Ueng, Y.-G.; Wang, J.-L,; Wann, G.-H.; Wu, K.-S. J. Chin. Chem. Soc. 1991, 38, 257. (e) Wei, C.-P.; Liao, C.-C. Tetrahedron Lett. 1991, 32, 4553. (f) Hwang, J.-T.; Liao, C.-C. Tetrahedron Lett. 1991, 32, 6583. (g) Hong, F.-T.; Lee, K.-S.; Liao, C.-C. Tetrahedron Lett. 1992, 33, 2155.

(10) (a) Liao, C.-C.; Lin, S.-Y.; Hsieh, H.-P.; Yang, P.-H. J. Chin. Chem. Soc. 1991, 38, 257. (b) Liao, C.-C.; Yang, P.-H. Tetrahedron Lett. 1992, 33, 5521. (c) Liao, C.-C.; Yang, P.-H. Handbook of Photochemistry and Photobiology, (Eds.: Horspool, W. M.; Song, P.-S.), CRC Press: Florida, 1995, Chapter 15.

(11) (a) Madej, S. L.; Gillispie, G. D.; Lim, E. C. Chem. Phys. 1978, 32, 1. (b) Boldridge, D. W.; Scott, G. W.; Spiglanin, T. A. J. Phys. Chem., 1982, 86, 1976. (c) Cundall, R. B.; Robinson, D. A. J. Chem. Soc., Faraday Trans. 2, 1972, 68, 1145.

(12) Chang, T.-H.; Chuang, C.-P.; Liao, C.-C.; Lin, H.-S.; Ueng, Y.-G. J. Chin. Chem. Soc. 1980, 27, 977.

(13) Tamura, Y.; Yakura, T.; Haruta, J.; Kita, Y. J. Org. Chem., 1987, 52, 3930.

(14) Chen, A.-A.; Chuang, J. G.; Villarante, N. R.; Liao, C.-C. accepted by J. Org. Chem.

(15) The effect of having a methyl group on the bridgehead turned out to be favoring the bridging accrosing the group, thus the steric effect of methyl group could be moderately ignored.

(16) Kopecky, J. Organic Photochemistry: A Visual Approach, VCH, Cambridge, U. K., 1992, 14.20, p. 220.

(17) BransonTM 5510 series, at “degas” setting.

(18) Detail information of rayonet reactor can be found at: http://www.rayonet.org/.

(19) Kopecky, J. Organic Photochemistry: A Visual Approach, VCH, Cambridge, U. K., 1992, 3.40, p. 43.

(20) 2.14 (s, 3H), 1.70 (s, 3H), 1.57 (s, 3H) for compound 76 and 1.92 (s, 3H), 1.52 (s, 6H) for compound 92, respectively.

(21) Frutos, L. M.; Sancho, U.; Castano, O. Org. Lett. 2004, 6, 1229.

(22) (a) Hoffmann, R.; Stohrer, W. D. J. Am. Chem. Soc. 1971, 93, 6941. (b) Sauer, J.; Bäuerlein, P.; Ebenbeck, W.; Brenzinger, R. D.; Gousetis, C.; Sichert, H.; Troll, T.; Wallfahrer, U. Eur. J. Org. Chem. 2001, 14, 2639.

(23) (a) Rattray, G.; Yang, J.; Gudmundsdottir, A. D.; Scheffer, J. R. Tetrahedron Lett. 1993, 34, 35. (b) Iwamura, M.; Tukada, H.; Iwamura, H. Tetrahedron Lett. 1980, 21, 4865.

(24) Zimmerman, H. E. in “Organic Photochemistry” Padwa, A. Ed., Marcel Dekker, New York, 1991, Vol. 11, p. 1.

(25) Bordwell, F. G.; Lynch, T. Y. J. Am. Chem. Soc. 1989, 111, 7558.
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