Title

熱解2,3,7-三氮-二環[3.3.0]辛-2-烯類衍生物中重排反應之研究

Translated Titles

Study on Rearrangement in Thermal Decomposition of 2,3,7-triazabicyclo[3.3.0]oct-2-ene Derivatives

DOI

10.6840/CYCU.2007.00240

Authors

陳文珊

Key Words

2,5-二氫砒咯 ; 重排 ; 自我氧化還原 ; 3,4-二取代砒咯 ; 1,2-氫轉移 ; 1,3-移位 ; 3,4-disubstituted pyrrole ; self-redox reaction ; 2,5-dihydropyrrole ; rearrangement ; 1,3-migration ; 1,2-hydrogen shift

PublicationName

中原大學化學研究所學位論文

Volume or Term/Year and Month of Publication

2007年

Academic Degree Category

碩士

Advisor

楊嘉喜

Content Language

繁體中文

Chinese Abstract

本研究利用2,3,7-三氮-二環[3.3.0]辛-2-烯在1號位置上接上COOCH3、COCH3、CN三種不同取代基再分別與甲基乙烯基酮、乙基乙烯基酮在7號氮上進行麥可加成(Michael addition)反應使其接上不同的取代基,之後將這些新合成出來的1-乙醯基-7-(3-氧代正丁基)-2,3,7-三氮-二環[3.3.0]辛-2-烯(1a)、1-甲氧羰基-7-(3-氧代正丁基)-2,3,7-三氮-二環[3.3.0]辛-2-烯(1d)與1-氰基-7-(3-氧代正丁基)-2,3,7-三氮-二環[3.3.0]辛-2-烯(1h)分別進行無氧下的高溫熱解反應,即可得本研究欲探討之重排化合物。 將一系列合成出來的2,3,7-三氧-二環[3.3.0]辛-2-烯類化合物,加入適量的對位二甲苯當作溶劑並架上迴流裝置,保持整個系統與外界隔絕下,進行140度的高溫熱解反應,反應時間為6個小時。待反應完全後去除溶劑,經由矽膠色層分析管柱純化分離即可得到此重排化合物(b)。 由實驗過程中我們可以推測出這一系列2,3,7-三氧-二環[3.3.0]辛-2-烯類化合物的熱解反應可經由(1)脫氮、(2)自我氧化還原、(3)脫水、(4)重排 四個步驟即可得到此重排化合物。而由實驗內容得知2,3,7-三氮-二環[3.3.0]辛-2-烯類化合物7號位置上的取代基是主要決定是否產生重排化合物的關鍵,唯有在7號位置上接上COR官能基,才會有重排化合物的產生。故可得知不論1號位置上接的是 COOR、COR 或 CN這三種的任何一種拉電子基,只要在7號位置上是COR官能基,在熱解之後都會有此重排化合物的產生,而在此重排過程中7號位置上的氮是經過1,3-位移的轉變而得到的,且是為一反式的烯基化合物。 而針對此重排化合物所推測的反應機制在經由許多的實驗驗證後發現結果並不符合我們的預期,所以對這個特別的重排反應的機制仍須再做進一步的研究探討。

English Abstract

7-(3-oxo- butyl)-2,3,7-triazabicyclo[3.3.0]oct-2-ene can be prepared by Michael addition of 2,3,7-triazabicyclo[3.3.0]oct-2-ene to Methyl vinyl ketone . Similarly, 7-(3-oxo-butyl)-2,3,7-triazabicyclo[3.3.0]oct-2-ene can be prepared. The thermal decomposition of these compounds under argon gave pyrrole as a product. The starting material underwent (1) denitrogenation, (2) self-redox reaction, (3) dehydration, and (4) rearrangement to give the final product. This rearrangement was observed no matter the substituent at 1-position was acetyl, methoxycarbonyl or cyano as long as the substituent at 7-position was RC(=O)CH2CH2-. Furthermore, the rearrangement involved 1,3-migration of the nitrogen atom in 7-position, and the substituent at the 7-position in the product was a trans alkenyl substituent. A mechanism was proposed to account for the reaction product. However, experiments designed to confirm the mechanism did not give positive results. Therefore, furthermore study has to be carried out to look into the reaction mechanism of this rearrangement.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學研究所
Reference
  1. (2) Schneider Manfred P., Crawford Robert J., Can.J.Chem.1970, 48, 628
    連結:
  2. (5) Seltzer Stanley, J.Am.hem.Soc.1961, 83, 2625
    連結:
  3. (6) Crawford Robert J.,Cameron Douglas M., Can.J.Chem.1967, 45, 691
    連結:
  4. (7) Allred Evan L.,Smith Richard Leon., J.Am.Chem.Soc.1967, 89, 7133
    連結:
  5. (10) Liliane Vo Quang, Henri Gaessler, and Yen Vo Quang, Angew.Chem.Int.Ed.Engl.1981, 20, 880
    連結:
  6. (16) Yi-Min She, Oleg Krokhin, Victor Spicer, Alexandre Loboda, Gideon Garland, Werner Ens, Kenneth G. Standing and John B. Westmore, Journal of the American Society for Mass Spectrometry 2007, 18, 1024
    連結:
  7. (1) 中原大學陳淑娟之碩士論文(民國八十二年六月)
  8. (3) Waldemar Adam, Nestor Carballeira, and De Lucchi, J.Am.Chem.Soc.1981, 103, 6406
  9. (4) Waldemar Adam, Thomas Oppenlander, and Gerald, J.Org.Chem. 1985, 50, 3303
  10. (8) Roth Wolfgang R.,Martin, Manfred., Tetrahedron Letters 1967, 23, 4695
  11. (9) Maliakel P. Balu, Hiriyakkanavar Ila and Hiriyakkanavar Junjappa, Tetrahedron 1990, 46, 6771
  12. (11) 中原大學王馨儀之碩士論文(民國九十六年六月)
  13. (12) Andrea Pace, Silvestre Buscemi, Nicolo Vivona, Arturo Silvestri, andGiampaolo Barone, J. Org. Chem. 2006, 71, 2740-2749
  14. (13) Takashi Ooi, Makoto Takahashi, Kanae Doda, and Keiji Maruoka, J. AM. CHEM. SOC. 2002, 124, 7640-7641
  15. (14) Calvin L. Stevens, Robert D. Elliott, and Bradley L. Winch, J.Am.Chem.Soc.1962, 85, 1464
  16. (15) Calvin L. Stevens, Irwin L. Klundt, Morton E. Munk, M. D. Pillai, J. Org. Chem. 1965, 30, 2967
  17. (17) 中原大學鍾慧容之碩士論文(民國八十六年六月)
  18. (18) 中原大學王瑞瑄之碩士論文(民國八十四年六月)