以含氟鏈聯吡啶鈀金屬錯合物在溫控系統下進行Suzuki 和Sonogashira耦合反應及相關研究

Using Fluorous Bipyridine Ligands for the Pdcatalyzed Suzuki and Sonogashira Reaction Under Thermomorphic Condition and Related Research

陳威順(Wei-Shung Chen)

指導教授 ： 呂良賜

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2009年)

摘要

我們氟素高科技實驗室一開始以4,4′二甲基聯吡啶為起始物，合成4,4′二溴二甲基聯吡啶前驅物。以一系列的含氟醇類和甲醇鈉反應形成一系列的氟醇鈉鹽親和試劑，再以此親和試劑和聯吡啶的前驅物反應後得到一系列含氟比例不同的含氟長鏈聯吡啶配位基。
以這一系列的含氟長鏈聯吡啶配位基和二氯二乙腈化鈀[PdCl2(CH3CN)2]攪拌後可以得到含氟長鏈聯吡啶鈀錯合物，經過核磁共振儀(NMR)、傅立葉轉換式紅外線光譜儀(FTIR)、快速原子撞擊式質譜儀(FAB/MS)還有X 光繞射的結晶分析鑑定其結構。
最後以這一系列的金屬嘗試在溫控(Thermomorphic System)系統下進行Suzuki 和Sonogashira 耦合反應，而溫控系統是藉由改變溫度來控制金屬錯合物對溶劑的溶解度來達到高溫時均相催化，低溫時異相分離的優點。最後並比較不同含氟比例聯吡啶鈀錯合物、有無添加輔助催化劑碘化亞銅、添加鹼的種類和使用量所造成的影響。
由於本實驗室之前的反應都是在探討四位置取代的含氟聯吡啶的效能，為了探討不同取代位置的含氟鏈聯吡啶的特性，所以便開始合成五位置取代的含氟鏈聯吡啶配位基和錯合物。

關鍵字

氟雙向系統 ； Sonogashira耦合反應 ； 含氟長鏈 ； 溫控

並列摘要

We used 4,4′-dimethyl-2,2′-bipyridine as the starting material to synthesize 4,4′-bis(bromomethyl)-2,2′-bipyridine. A series of fluorous alcohols were reacted with sodium methoxide to generate a series of fluorous alkoxides, which as a nucleophile, reacted with 4,4′-bis(bromo-methyl)-2,2′-bipyridine to yield various fluorous bipyridine ligands (4,4′-bis(RfCH2OCH2)-2,2′-bipyridine) {Rf = -CnF2n+1 , -CnF2nH}.
The fluorous bipyridine ligands were stirred with PdCl2(CH3CN)2 to produce easily the fluoroalkylated bipyridine palladium complexes, which were characterized with NMR, FTIR, FAB/MS, and X-ray diffraction.
The series of fluorous bipyridine palladium complexes were applied in the Suzuki and Sonogashira reactions under a thermomorphic system. The advantage of a thermomorphic system is a homogeneous catalysis at high temperature, and the easy separation of product mixtures from the fluorous catalyst at low temperature. We measured the reactivity due to different fluorous bipyridine palladium complexes, different bases and different treatments, for example, with copper iodide or copper-free.
Most of our early experiments were based on the 4,4′-disubstituted bipyridine derivatives. We have extended our interests to bipyridines with fluoro-ponytails at different positions. According by the 5,5′-bis(fluoro-ponytailed) bipyridine ligand were prepared and the corresponding complexes were studied.

並列關鍵字

FBS ； Sonogashira reaction ； fluorous pony tail ； thermomorphic

參考文獻

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