特殊氟鏈螯合劑及其金屬錯合物之合成、結構與反應性

Synthesis, Structure and Reactivity of Fluorous Pyridine and Their Metal Complexes

林冠宇(Kuan-Yu Lin)

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(2014年)

https://doi.org/10.6841/NTUT.2014.00629

摘要

合成特殊含氟吡啶[4-RfCH2OCH2-pyridine，Rf = CF2Cl, CF3, C2F5, C3F7, C11F23]、和含氟聯吡啶[4,4'-RfCH2OCH2-bipyridine，Rf = C9F19, C10F21, C11F23]、 [-RfCH2OCH2-bipyridine，Rf =C9F19, C10F21, C11F23]並將長氟鏈的化合物作為催化劑成功地運用於磷-麥可加成反應(Phospha-Michael addition)並且表現出非常良好的反應性。在高溫時，催化劑能在有溶液裡溶解並且有效地催化反應的進行。而降低至室溫時，催化劑沉澱稀出而有效得分離催化劑與反應溶液來回收再利用，催化劑在經過8次的催化反應後依然具有很好的反應性。透過NMR(1H、13C、19F)、FTIR、GC/MS鑑定之。
含氟吡啶也能與K2PtCl4形成錯合物，透過NMR(1H, 13C, 19F)、FTIR、高解析質譜儀(HR-FAB)進行鑑定。

關鍵字

含氟吡啶螯合劑 ； 均相催化異相分離 ； 鈀錯合物 ； Phospha-Michael 加成 ； 觸媒回收

並列摘要

Synthesis of fluorous pyridine [4-RfCH2OCH2-pyridine，Rf = CF2Cl, CF3, C2F5, C3F7, C11F23] or fluorous bipyridine [4,4'-RfCH2OCH2-bipyridine、5,5'-RfCH2OCH2-bipyridine，Rf =C9F19, C10F21, C11F23] which has been usd as a ligand and a catalyst for the Phospha-Michael addition of diisopropyl phosphite to α, β-unsaturated malonates has been successfully carried out and showed the very good reactivity and recyclability. In polar solvents, the long fluorous chain-containing pyridine demonstrated the good thermophoric property which means the solubility of catalyst increases dramatically with the increasing temperature. At the elevated temperature, catalyst was dissolved and homogeneous catalysis was underway. After the reaction, the catalyst was precipitated out when the reaction mixture was cooled down to room temperature, and hence it was regarded as heterogeneous catalysis separation and reusing the recoverable catalyst. Then the fluorinated pyridine-catalyzed Phospha-Michael addition has been successfully carried out and recovered catalyst has been reused for a total of 8 times with good yieldings. The catalyst and products were characterized by FT-IR, GC/MS and NMR.
The Long-chain fluorous pyridine has also been used to react with K2PtCl4 to form the novel pyridine containing Pt complexes, which were also characterized by FT-IR, FAB, and NMR.

並列關鍵字

Fluorous pyridine ligands ； Heterogenization of homogeneous catalyst ； Catalyst recycling ； Phospha-Michael addition ； Platinum complex

參考文獻

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