(3.238.99.243) 您好!臺灣時間:2021/05/17 00:20
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:歐陽承欣
研究生(外文):Cheng-Hsin Ou Yang
論文名稱:二價銅促進1,2,3-三嗪與二級胺之親核性加成氧化反應
論文名稱(外文):Aerobic Copper(II)-Promoted Oxidative Nucleophilic Addition of 1,2,3-Triazine with Secondary Amines
指導教授:謝俊結侯敦仁
指導教授(外文):Jiun-Jie ShieDuen-Ren Hou
學位類別:碩士
校院名稱:國立中央大學
系所名稱:化學學系
學門:自然科學學門
學類:化學學類
論文出版年:2020
畢業學年度:108
語文別:英文
論文頁數:111
中文關鍵詞:123-三嗪二級胺親核性加成氧化反應二價銅
外文關鍵詞:123-TriazineSecondary AminesNucleophilic AdditionOxidative reactionCopper(II)Aerobic
相關次數:
  • 被引用被引用:0
  • 點閱點閱:31
  • 評分評分:
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:0
1,2,3-三嗪(5)被視為缺電子的含三氮六員雜環化合物,由於其化學性質不穩定並且製備合成不易,是所有三嗪類化合物家族中最晚被研究的,相關研究文獻並不多。近期探討1,2,3-三嗪(5)反應活性的研究有逐步發展的趨勢,例如在1,2,3-三嗪(5)的4、5、6號位置引入推電子基或是拉電子官能基進行修飾,再透過逆向狄耳士–阿爾德反應來進行環加成反應,或者利用親核試劑在C4或C5位置進行親核加成反應。在本篇論文中,我們以乙腈作為溶劑,使用二級胺與1,2,3-三嗪(5)進行親核加成反應,反應過程時會脫去一分子氮氣,形成亞胺中間體,搭配二價醋酸銅與氧氣的反應條件,將亞胺中間體進一步氧化形成trans-β-acrylonitriles產物。優化後的反應條件在不同種類的二級胺與1,2,3-三嗪(5)進行親核加成氧化反應皆有不錯的產率。而在後續的實驗中我們也發現了反應在含水條件下可能對亞胺中間體進行水解導致產率降低,我們也將氧氣換成氮氣後觀察氧氣對銅離子進行氧化反應的影響。而這個好氧銅催化反應也幫助我們拓展1,2,3-三嗪在有機化學中的應用性。
Triazines are three nitrogen atoms-containing six-membered ring compounds. The isomers of triazines can be distinguished from each other by the positions of their nitrogen atoms, which are referred to as 1,2,3-triazines, 1,2,4-triazines, and 1,3,5-triazines, respectively. 1,2,3-Triazines are classified as electron-deficient heterocycles that are the least investigated because their ring system is considered to be the least stable and their synthetic routes are limited. Recent, several studies have demonstrated the reactivity of selected 1,2,3-triazines to participate in inverse electron demand Diels-Alder reactions with various amine-related dienophiles. In this thesis, we present a user-friendly and effective synthesis of trans-β-acrylonitriles based on the oxidative nucleophilic addition of secondary amines to 1,2,3-triazine (5). The addition of secondary amines, including cyclic amines and heterocyclic amines as well as asymmetric amines, to 1,2,3-triazine (5) under mild reaction conditions (CH3CN, 25‒60 oC, 3‒60 h) by oxidation of Cu(II) species with using O2 to fulfill the promoted cycle. The reaction proceeds by amine nucleophilic addition to C-4 of the 1,2,3-triazine core with highly regioselectivity, in situ loss of nitrogen, and subsequent imine oxidation to generate trans-β-acrylonitriles. Further studies on the scope and synthetic applications of this reaction are currently underway.
摘要 i
ABSTRACT ii
誌謝 iii
目錄 iv
圖目錄 vi
表目錄 viii
縮寫表 ix
第一章 緒論 1
1-1 前言 1
1-2 雜環化合物 2
1-3 1,2,3-三嗪之相關研究 5
1-3-1 1,2,3-三嗪的環加成反應 5
1-3-2 1,2,3-三嗪的親核反應 15
1-4 高價碘化合物 17
1-5 有氧銅催化反應 18
1-5-1 烯烴的好氧銅催化 19
1-5-2 炔胺的好氧銅催化 21
第二章 實驗結果與討論 23
2-1 起始物1,2,3-三嗪的合成 23
2-2 高價碘試劑氧化1,2,3-三嗪反應 23
2-2-1 高價碘試劑氧化1,2,3-三嗪反應之溶劑篩選 24
2-2-2 高價碘試劑氧化1,2,3-三嗪反應之氧化劑篩選 25
2-3 好氧銅促進反應 27
2-3-1 溶劑之篩選 28
2-3-2 促進劑當量數之篩選 29
2-3-3 促進劑之篩選 30
2-3-4 控制實驗 32
2-4 優化條件 34
2-5 反應物範圍測試 35
2-6 反應機制討論 40
第三章 結論 42
第四章 實驗部分 43
4-1 實驗儀器 43
4-1-1 核磁共振光譜儀(Nuclear Magnetic Resonance Spectroscopy, NMR) 43
4-1-2 高解析質譜儀 43
4-1-3 FTIR近紅外光譜儀 44
4-1-4 熔點測定儀 44
4-1-5 減壓式迴旋濃縮儀 44
4-2 實驗藥品 44
4-3 TLC薄層色層分析 44
4-4 合成步驟 45
參考文獻 57
附錄 61
[1] Moss, G. P.; Smith, P. A. S.; Tavernier, D. “Glossary of class names of organic compounds and reactive itermediates based on structure.” Pure Appl. Chem. 1995, 67, 1307‒1375.
[2] Bhalla, V.; Grimm, P. C.; Chertow, G. M.; Pao, A. C. “Melamine nephrotoxicity: an emerging epidemic in an era of globalization.” Kidney Int. 2009, 75, 774‒779.
[3] Chien, C. Y.; Wu, C. F.; Liu, C. C.; Chen, B. H.; Huang, S. P.; Chou, Y. H.; Chang, A. W.; Lee, H. H.; Pan, C. H.; Wu, W. J.; Shen, J. T.; Chang, M. Y.; Huang, C. H.; Shiea, J.; Hsieh, T. J.; Wu, M. T. “High melamine migration in daily-use melamine-made tableware.” J. Hazard. Mater. 2011, 188, 350‒356.
[4] Huthmacher, K.; Most, D. “Cyanuric Acid and Cyanuric Chloride.” In Ullmann's Encyclopedia of Industrial Chemistry, 7th ed.; Wiley-VCH: Weinheim, Germany, 2006.
[5] El-Faham, A.; Osman, S. M.; Al-Lohedan, H. A.; El-Mahdy, G. A. “Hydrazino-methoxy-1,3,5-triazine derivatives excellent corrosion organic inhibitors of steel in acidic chloride solution.” Molecules 2016, 21, 714-727.
[6] Zhao, Y.; King, G.; Kwan, M. H. T.; Blacker, A. J. “A mild and selective method for the catalytic hydrodeoxygenation of cyanurate activated phenols in multiphasic continuous flow.” Org. Process Res. Dev. 2016, 20, 2012‒2018.
[7] Shi, B.; Lewis, W.; Campbell, I. B.; Moody, C. J. “A concise route to pyridines from hydrazides by metal carbene N−H insertion, 1,2,4-Triazine Formation, and Diels−Alder Reaction.” Org. Lett. 2009, 11, 3686‒3688.
[8] Quiñones, R. E.; Glinkerman, C. M.; Zhu, K.; Boger, D. L. “Direct synthesis of β-aminoenals through reaction of 1,2,3-triazine with secondary amines.” Org. Lett. 2017, 19, 3568‒3571.
[9] Anderson, E. D.; Boger, D. L. “Inverse electron demand Diels–Alder reactions of 1,2,3-triazines: pronounced substituent effects on reactivity and cycloaddition Scope.” J. Am. Chem. Soc. 2011, 133, 12285‒12292.
[10] Itoh, T.; Ohsawa, A.; Okada, M.; Kaihoh, T.; Igeta, H. “Reaction of 1,2,3-triazine with dieneophile.” Chem. Pharm. Bull. 1985, 33, 3050‒3052.
[11] Okatani, T.; Koyama, J.; Tagahara, K.; Suzuta, Y. “Synthesis of sesquiterpene alkaloids, guaipyridine: epiguaipyridine and related compounds.” Heterocycles 1987, 26, 595‒597.
[12] Okatani, T.; Koyama, J.; Suzuta, Y.; Tagahara, K. “The effects of solvent and temperature on the orientation of cycloaddition reaction of 1,2,3-triazine with enamines: its application to the synthesis of alkaloids. onychine and 6-methoxyonychine.” Heterocycles 1988, 27, 2213‒2217.
[13] Okatani, T.; Koyama, J.; Tagahara, K. “Modified synthesis of monocyclic 1,2,3-triazine and cycloaddition reaction with enamine: the application to the synthesis of alkaloids, tortuosamine, N-formyltortuosamine and N-acetyltortuosamine.” Heterocycles 1989, 29, 1809‒1814.
[14] Itoh, T.; Okada, M.; Nagata, K.; Yamaguchi, K.; Ohsawa, A. “The ring transformation of 1, 2, 3-triazines.” Chem. Pharm. Bull. 1990, 38, 2108‒2111.
[15] Anderson, E. D.; Duerfeldt, A. S.; Zhu, K.; Glinkerman, C. M.; Boger, D. L. “Cycloadditions of noncomplementary substituted 1,2,3-triazines.” Org. Lett. 2014, 16, 5084‒5087.
[16] Glinkerman, C. M.; Boger, D. L. “Cycloadditions of 1,2,3-triazines bearing C5-electron donating substituents: robust pyrimidine synthesis.” Org. Lett. 2015, 17, 4002‒4005.
[17] Ohsawa, A.; Kaihoh, T.; Igeta, H. “The reaction of 1,2,3-triazines with Grignard reagents.” J. Chem. Soc., Chem. Commun. 1985, 20, 1370‒1371.
[18] Itoh, T.; Nagata, K.; Kaihoh, T.; Okada, M.; Kawabata, C.; Arai, H.; Ohnishi, H.; Yamaguchi, K.; Igeta, H.; Ohsawa, A.; Iitaka, Y. “The reactivity of monocyclic 1,2,3-triazine.” Heterocycles 1992, 33, 631‒639.
[19] Cavani, F.; Teles, J. H. “Sustainability in catalytic oxidation: an alternative approach or a structural evolution.” ChemSusChem 2009, 2, 508‒534.
[20] Davies, H. M. L.; Manning, J. R. “Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion.” Nature 2008, 451, 417‒424.
[21] Constable, D. J. C.; Dunn, P. J.; Hayler, J. D.; Humphrey, G. R.; Leazer, Jr. J. L.; Linderman, R. J.; Lorenz, K.; Manley, J.; Pearlman, B. A.; Wells, A.; Zaks, A.; Zhang, T. Y. “Key green chemistry research areas‒a perspective from pharmaceutical manufacturers.” Green Chem. 2007, 9, 411‒420.
[22] Gligorich, K. M.; Sigman, M. S. “Recent advancements and challenges of palladium II-catalyzed oxidation reactions with molecular oxygen as the sole oxidant.” Chem. Commun. 2009, 26, 3854‒3867.
[23] Stahl, S. S. “Palladium-catalyzed oxidation of organic chemicals with O2.” Science 2005, 309, 1824‒1826.
[24] Allen, S. E.; Walvoord, R. R.; Padilla-Salinas, R.; Kozlowski, M. C. “Aerobic copper-catalyzed organic reactions.” Chem. Rev. 2013, 113, 6234‒6458.
[25] Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. “Metal organic frameworks as efficient heterogeneous catalysts for the oxidation of benzylic compounds with t-butylhydroperoxide.” J. Catal. 2009, 267, 1‒4.
[26] Barton, D. H. R.; Beviere, S. D.; Hill, D. R. “The functionalization of saturated hydrocarbons part XXIX. Application of tert-butyl hydroperoxide and dioxygen using soluble Fe(III) and Cu(II) chelates.” Tetrahedron 1994, 50, 2665‒2670.
[27] Glaser, C. “Beiträge zur kenntniss des acetenylbenzols.” Ber. Dtsch. Chem. Ges. 1869, 2, 422‒424.
[28] Hay, A. S. “Oxidative coupling of acetylenes.” J. Org. Chem. 1962, 27, 3320‒3321.
[29] Hamada, T.; Ye, X.; Stahl, S. S. “Copper-catalyzed aerobic oxidative amidation of terminal alkynes: efficient synthesis of ynamides.” J. Am. Chem. Soc. 2008, 130, 833‒835.
[30] Laouiti, A.; Rammah, M. M.; Rammah, M. B.; Marrot, J.; Couty, F.; Evano, G. “Copper-catalyzed oxidative alkynylation of diaryl imines with terminal alkynes: a facile synthesis of ynimines.” Org. Lett. 2012, 14, 6‒9.
[31] Hynes, J.; Doubleday, W. W.; Dyckman, A. J.; Godfrey, J. D.; Grosso, J. A.; Kiau, S.; Leftheris, K. “N-Amination of pyrrole and indole heterocycles with monochloramine (NH2Cl).” J. Org. Chem. 2004, 69, 1368‒1371.
[32] Mondal, S.; Samanta, S.; Jana, S.; Hajra, A. “(Diacetoxy)iodobenzene-mediated oxidative C−H amination of imidazopyridines at ambient temperature.” J. Org. Chem. 2017, 82, 4504‒4510.
電子全文 電子全文(網際網路公開日期:20250721)
連結至畢業學校之論文網頁點我開啟連結
註: 此連結為研究生畢業學校所提供,不一定有電子全文可供下載,若連結有誤,請點選上方之〝勘誤回報〞功能,我們會盡快修正,謝謝!
QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top