含氮雜環碳烯一價銅金屬錯化合物的合成、鑑定與 Acetylation 反應與 Huisgen 環化反應的催化應用

Synthesis and Characterization of N-Heterocyclic Carbene Copper(I) Complexes. The Catalytic Application on Huisgen Cycloaddition and Acetylation Reactions.

李岳峰(Yue Feng Li)

指導教授 ： 于淑君

國立中正大學/理學院/化學暨生物化學系/碩士(2014年)

摘要

中文摘要
銅具有低毒性且地殼含量豐富的優勢，在用途上它可以作為生物體所需的微量膳食礦物質，也可製成容易回收的工業製品，在二十世紀時期，它亦成功用來作為觸媒的使用。
本論文成功以一鍋化的方法分別將兩種咪唑鹽 (1) 和 (4) 與三氟甲磺酸銅 (Cu(OTf)2) 和叔丁醇鈉 (NaOtBu) 反應，得到兩種綠色化學金屬觸媒: [Cu(bmim)2](OTf) (2) 與 [Cu(Mesbim)2](OTf) (5)。為了要確定此兩種觸媒的結構，我們分別將兩觸媒以電噴灑離子化質譜儀 (ESI-Mass)、核磁共振的氫、碳及氟譜 (1H NMR、13C NMR and 19F NMR)、紅外線光譜儀 (IR) 及原子吸收光譜儀 (AA)來輔佐證明。此外，本論文另外量測觸媒 [Cu(Mesbim)2](OTf) (5) 的循環伏安法 (CV) 與 X 射線光電子能譜 (XPS) 與文獻做比較，確認觸媒的價數與電化學性質。由質譜數據資料顯示，觸媒 (2) 與 (5) 推測為一價銅配位上兩含碳雜環碳烯的結構 ([Cu(NHC)2]+)。而觸媒 (5) 的 X 射線光電子能譜的數據，銅的內層能階 (2p3/2) 的束縛能為 931 電子伏特，與一價銅的 X 射線光電子能譜的數據相符合，因此確認催化劑為一價銅。此外，核磁共振氫譜、紅外線光譜儀及原子吸收光譜儀則可以輔佐鑑定觸媒的純度與結構。
醇類的乙醯化是有機合成中使用頻率高且重要的反應。本論文使用 2 與 5 兩種觸媒來催化各種醇類、苯酚與乙酸酐的反應，在催化劑量為 2 mol%，無外加溶劑且溫度為 60 ℃ 的條件下反應 3 小時可得到高產率。此外，以微波輔助此催化反應可大幅減少反應時間且同時維持高產率。
除上述反應外，本論文同時以 2 與 5 兩種觸媒來催化疊氮化物 (azide) 與炔類 (alkyne) 的環化反應，在催化劑量為 1 mol%，無外加溶劑且無需外加能量的條件下 2 小時內便可得到大於 95 % 的產率，僅觸媒 (5) 催化辛炔與疊氮化物時需加熱至 50 ℃ 才能維持好的產率。此外根據實驗結果我們發現當炔基的酸性越強，此環化反應的速度也會跟著提升。

關鍵字

一價銅

並列摘要

Abstract
Copper is an earth-abundant and non-toxic metal element. It is essential to all living organisms as trace dietary minerals. In addition, it is by far one of the most common metals in industrial use and the most recycled metals. Their chemistry as being catalysts has been established since at the turn of the twentieth century.
In this present study, two green catalysts copper(I) complexes {[Cu(bmim)2](OTf) (2) and [Cu(Mesbim)2(OTf)] (5)} were synthesized from the direct reaction of imidazolium salts {(bmim)HBr (1) and (Mesbim)HBr (4)} with copper (II) triflate in the presence of NaOtBu. The structures of 2 and 5 were analyzed by using ESI-mass, 13C NMR, 1H NMR, 19F NMR, IR and AA spectroscopy. The structure of 5 was also analyzed by using CV and XPS. According to the mass spectral data, the compositions of 2 and 5 were determined to be [Cu(bmim)2]+ and [Cu(Mesbim)2]+. The XPS data for 5 also gave a characteristic binding energy of 931 eV for Cu(I) 2p3/2. Finally, the 1H NMR, AA and IR spectral data all confirmed the structure and purity of 2 and 5.
The acetylation of alcohols is among the most frequently used processes in organic synthesis. A series of acetylation reactions of acetic anhydride and alcohols were catalyzed by 2 and 5 with a catalyst loading of 2 mol %. These catalyses were carried out under solventless conditions at 60 ℃ to give high yields in 3 hours. Furthermore it was demonstrated that these catalytic reactions can be further accelerated under microwave flash heating conditions.
A series of cycloaddition reactions of azides (R─N3) and two kinds of alkynes (phenyl acetylene and octyne) with a catalyst loading of 1 mol % of 2 and 5 were carried out under solventless conditions at ambient temperature to give the corresponding cycloaddition products with > 95% yields in 2 hours, only the actalysis of octyne and azide by 5 need to be carried out at elevated temperature of 50 ℃ in order to get high yields. It was found that the more acidic of the alkyne was, the more reactive the cycloaddition became.

並列關鍵字

Copper(I)

參考文獻

(1) Faraday, M. Philos. Trans. R. Soc. London 1834, 124, 55.

Applications of Organotransition Metal Chemistry ’; Mill Valley,

(5) International Copper Association.

(7) Ullmann, F.; Bielecki, J. Ber. dtsch. chem. Ges. 1901, 34, 2174.

(8) Lindley, J. Tetrahedron 1984, 40, 1433.