利用多面體的氧化亞銅奈米晶體進行光催化的氧化環化硫代醯胺之反應

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研究生：	王冠茹 Wang, Guan-Ru
論文名稱：	利用多面體的氧化亞銅奈米晶體進行光催化的氧化環化硫代醯胺之反應 Photocatalytic Oxidative Cyclization of Aromatic Thioamides Catalyzed by Cu2O Rhombic Dodecahedra
指導教授：	黃暄益 Huang, Hsuan-Yi
口試委員:	莊敬 Chuang, Gary-Jing 吳彥谷 Wu, Yen-Ku
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2024
畢業學年度：	112
語文別：	英文
論文頁數：	78
中文關鍵詞：	光催化、材料、有機合成、氧化亞銅
外文關鍵詞：	materials, organic synthesis, copper oxide, photocatalysis
相關次數：	點閱：40 下載：0
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光催化的有機氧化反應是一種新穎且綠色的合成策略。本研究利用氧化亞銅奈米晶體作為光催化劑，用於硫代醯胺的氧化環化反應。在氧化亞銅材料具備合成容易、合成時間短、合成成本低等優點。控制實驗中可知光源、氧氣及光催化劑對於反應的重要性，並且在最佳條件篩選下，四氫呋喃為最佳溶劑。當用具不同晶面的氧化亞銅立方體、八面體以及菱形十二面體奈米晶體為催化劑，結果具{110}面的菱形十二面體氧化亞銅奈米晶體的催化效果最好，產率可達 94%。我們也將該實驗條件用於帶有不同官能基的硫代醯胺進行氧化環化反應，發現不同官能基團都可以有不錯的產率。最後根據自由基捕捉實驗以及 EPR 實驗提出可能的機制。

Catalytic organic oxidation through photocatalysis represents a novel and environmentally friendly synthetic strategy. In this study, copper oxide nanocrystals were employed as the photocatalyst for the oxidative cyclization of thioamides. The advantages of copper oxide materials include ease of synthesis, short synthesis time, and low synthesis cost. Control experiments revealed the crucial role of light source, oxygen, and photocatalyst in the reaction. Under the optimized conditions, tetrahydrofuran was identified as the best solvent. When using copper oxide cubes, octahedra, and rhombic dodecahedra as catalysts, it was found that rhombic dodecahedra exhibited the best catalytic performance, achieving a yield of up to 94%. The experimental conditions were also applied to oxidative cyclization reactions of thioamides with different functional groups, demonstrating promising yields for various functional groups. Finally, a possible mechanism was proposed based on free radical capture experiments and electron paramagnetic resonance (EPR) experiments. This study highlights the innovative and green nature of photocatalytic organic oxidation reactions and establishes a foundation for further development of environmentally friendly synthetic strategies and applications of copper oxide nanocrystals as efficient photocatalysts.

論文摘要.........................................................................................................................I
Abstract......................................................................................................................... II
誌謝..............................................................................................................................III
Table of Contents.........................................................................................................IV
List of Figures..............................................................................................................VI
List of Table ..............................................................................................................VIII
List of Schemes............................................................................................................IX
List of Spectrum............................................................................................................X
1. Introduction................................................................................................................1
1.1 Cuprous oxide and facet effects.......................................................................1
1.2 Applications of cuprous oxide in organic chemistry........................................5
1.3 Applications of 1,2,4-thiadiazoles..................................................................10
1.4 Thioamide cyclization for 1,2,4-thiadiazoles................................................. 11
1.5 Covalent organic frameworks as photocatalysts............................................13
2. Research Goal..........................................................................................................17
3. Experiment Section..................................................................................................18
3.1 Instrumentation ..............................................................................................18
3.2 Chemicals.......................................................................................................19
3.3 Synthesis of polyhedral Cu2O nanocrystals...................................................20
3.4 Calculations of particle weights for photocatalytic performance comparison
..............................................................................................................................22
3.5 Cu2O nanocrystal-photocatalyzed oxidative cyclization of thioamides........24
3.6 Trapping experiment......................................................................................26
3.7 Electron paramagnetic resonance experiment................................................32
V
4. Result and Discussion..............................................................................................34
4.1 The shapes and sizes of Cu2O nanocrystals...................................................34
4.2 Photocatalytic oxidative cyclization of thioamides.......................................37
4.3 Mechanism study ...........................................................................................45
4.4 Proposed mechanism .....................................................................................49
5. Conclusion ...............................................................................................................50
6. Spectroscopic Data of Isolated Products..................................................................51
7. References................................................................................................................55

                                

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