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  • 學位論文

可回收之鈀觸媒催化Stille Coupling 反應

Recyclable Palladium Bipyridyl Complexes Catalyzed Stille Coupling Reaction

指導教授 : 蔡福裕

摘要


摘 要 論文名稱:可回收之鈀觸媒催化 Stille Coupling 反應 頁數:108 校所別:國立台北科技大學有機高分子研究所 畢業時間:九十五學年度第二學期 學位:碩士 研究生:張芬萍 指導教授:蔡福裕 關鍵詞: 中孔洞材料,鈀錯合物,可回收催化劑,Stille coupling 過渡金屬鈀催化 Organotin 及 Aryl halides 的反應是形成碳-碳鍵一種十分有效的方法,基於此考量本實驗室發展出可回收及高效率之水相、固相鈀錯合物觸媒進行Stille coupling。 第一部份,本研究選擇二氧化矽的中孔洞材料作為擔體,我們先合成含bipyridine配位基之鈀金屬錯合物,再以後修飾法將其修飾至擔體 ( NS- MCM- 41 )上。此 NS-MCM-41-Pd 的顆粒大小約 100 nm 、且具有蟲洞結構,能增進反應系統中之分散性,並且具高表面積 ( 588 m2/g ) 和相當狹宰之孔道分布 ( 2.3 nm ),使其成為優越之非均相觸媒。由於, NS-MCM-41 與鈀錯合物是以共價鍵形式結合而成,在催化反應進行時,可有效降低鈀金屬之流失,且觸媒再回收使用能力極佳,至少可重複循環反應十次。經由原子分析儀器鑑定,顯示鈀金屬流失量僅 0.3 ppm 。 另ㄧ研究方向,利用本實驗室所研發的可回收及高效率之水相鈀觸媒 ( cationic 2,2’- bipyridyl palladium (II) ) 在水中及空氣下進行 Stille coupling 。過渡金屬催化的偶合反應多數是使用有機溶劑並於惰性氣體下進行反應,我們突破傳統以水作為溶劑代替有毒、易燃、且價格昂貴的有機溶劑,此項突破有效地節省經費支出及降低對環境造成之污染。以 cationic 2,2’- bipyridyl palladium (II) 催化 Organotin 及 Aryl halides 之反應可獲得極佳之反應性,且最高之 TON 值可達到 172,000 。

並列摘要


ABSTRACT Title:Recyclable Palladium Bipyridyl Complexes Catalyzed Stlle Coupling Reaction School:National Taipei University of Technology Pages:108 Department:Institute of Organic and Polymeric Materials Time:July, 2007 Degree:Master Researcher:Fen-Ping Chang Advisor:Fu-Yu Tsai Keywords : mesoporous material, palladium complex, recyclable catalyst, Stille coupling The palladium catalyzed cross-coupling of organotin compounds with aryl halides has appeared as one of the most significant methods for the catalytic carbon-carbon bond formation. Therefore, we developed solid-phase and aguoues-phase of palladium (II) bipyridyl complexes catalysis as efficient and recyclable catalysts for the Stille coupling. This thesis is collected of two parts. In the first part, we choose mesporous silica materials as support. The nano-sized mosoporous silica (NS- MCM-41) with worm- hole-like mesostructure was prepared for the grafting of palladium bipyridyl complexes inside the channels. This NS-MCM-41-Pd has uniform pore size ( 2.3 nm ) and high surface area ( 588 m2/g ) . The strong covalent bond between NS- MCM-41 and Palladium complex allows the recovery and recycling of the supported catalysts at least for ten cycles. Atomic absorption analysis of the reaction solutions shows that there is only less 0.3 ppm of Pd leaching into the solutions. In the second part, we develop a novel water-soluble cationic 2,2’- bipyridyl palladium (II) complex to play as a recyclable and extremely active catalyst for Stille reaction in water and air. Metal-catalyzed cross-coupling reactions are usually carried out in organic solvent under inert gas conditions due to the instability of the catalysts. The replacement of expensive, toxic, and combustible organic solvents by water is highly attractive for decreasing costs and pollution. A variety of aryl halides were coupled with organotin compounds efficiently to afford the corresponding cross-coupling products in moderate to excellent yields. The turnover numbers was up to 172,000 for the Stille coupling reaction in water.

參考文獻


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