含氮雜環碳烯一價銀金屬錯化合物的合成、鑑定與催化應用

Synthesis, Characterization and Catalytic Applications of N-Heterocyclic Carbene Silver(I) Complexes.

林羲尹(Hsi-Yin Lin)

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(2015年)

摘要

銀金屬的應用已有數千年的歷史，銀具有低毒性及地殼含量豐富的優點，其在貴重金屬當中價格相對便宜，同時易於回收再利用，因而在觸媒化學上具有高度的應用價值。
本篇論文成功的以簡單的方法將三種含氮雜環碳烯 (Hmim)HPF6 (2) 、 (2-MePybim)HPF6 (5) 和 (Mesbim)HPF6 (8) 與氧化銀反應，得到三種銀金屬觸媒 [Ag(hmim)2][PF6] (9) 、[Ag(2-MePybim)][PF6] (10) 以及 [Ag(Mesbim)CH3CN][PF6] (11)，並且利用核磁共振的氫、與碳 (1H NMR and 13C NMR)、紅外線光譜儀 (IR) 、電噴灑離子化質譜儀 (ESI-Mass) 、原子吸收光譜儀 (AA) 以及元素分析 (EA) 來進行定性與定量的結構組成鑑定。
多分子式的反應在有機合成上是極為重要的反應，它可將繁雜的合成步驟大幅度簡化， A3 偶合反應便是其中之一。本篇論文使用銀錯化合物 (9) 、 (10) 及 (11) 來催化A3 偶合反應，將醛類、苯乙炔及吡咯烷 (pyrrolidine) 在100 oC 下，加入 4 mol% 催化劑，反應 30 分鐘即可得到良好的轉化率 (conversion) ，並利用微波輔助催化，可大幅縮短反應時間，同時探討及改善文獻中未曾研究過的轉化率與產率的落差。
另外本篇也以 (9) 、 (10) 及 (11) 三種觸媒催化胺類與丙炔酸乙酯 (ethyl propiolate) 的氫胺化反應，在催化劑量為 4 mol% ，溫度 60 oC 下反應 4 小時，即可得到高的產率，並同時利用微波輔助大幅度縮短反應時間以提升能源使用效率。
藉由以上兩種有機反應，我們成功地開發了銀金屬與含氮雜環碳烯在均相催化反應上的應用。

關鍵字

含氮雜環碳烯 ； 一價銀 ； 催化

並列摘要

Silver was used by human for thounds of year. It is a low toxic and earth abundant metal. Furthermore, silver is much cheaper than most of noble metals and can be recycled easily. Therefore, silver-catalyzed organic reactions have attracted attention recently.
In this present study, we successfully synthesized three silver(I) N-heterocyclic carbene complexes (NHCs), [Ag(hmim)2][PF6] (9), [Ag(2-MePybim)][PF6] (10), and [Ag(Mesbim)CH3CN][PF6] (11), by direct reaction of Ag2O and imidazolium salts, (Hmim)HPF6 (2), (2-MePybim)HPF6 (5), and (Mesbim)HPF6 (8). And all 9, 10 and 11 were characterized by 1H NMR, 13C NMR, ESI-mass, FT-IR, AA and EA spectroscopies.
Muliticomponent reactions (MCRs) have been established as a extremely important processes in organic synthesis. And the aldehydes, alkynes, and amine coupling (A3 coupling) is one of them, which gives coupling products, propargylamines, as major skelentins for the preparations of many biologically active natural materials. A series of A3 coupling reaction of aldehydes, pyrrolidine, and phenylacetylene were catalyzed by 9, 10 and 11 with a catalyst loading of 4 mol% at 100 oC to gives high conversion in 30 minutes. Furthermore, we also demonstrated that the coupling reaction can be further accelerated under microwave flash heating conditions. By this, we first studied that conversion and yield are not consistent in A3 coupling in more detail.
In addition, a series of hydroamination reaction of amine and ethyl propiolate with a catalyst loading of 4 mol% of 9, 10 and 11 were also carried out at 60 oC to give corresponding products with high yiled in 4 hours. And can be further accelerated under microwave flash heating conditions in the same way.

並列關鍵字

N-Heterocyclic Carbene ； Silver(I) ； Catalytic

參考文獻

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