- 學位論文
含氟長鏈雙吡啶Pd金屬錯合物之Heck以及Suzuki反應研究
New Bis(fluoro-ponytailed) Bipyridine Ligands for the Pd-catalyzed Heck-type and Suzuki-type Reactions under Fluorous Biphasic and Thermomorphic conditions
摘要
我們以4,4’-bis(bromomethylene)-¬2,2′-bpy 以及含氟鏈的醇類合成出一系列的含氟長鏈雙吡啶之取代基，其中以其中幾種含氟比例較高的衍生物(4,4’-bis(RfCH2OCH2)-2,2’-bpy)，{Rf = n-C8F17(1a), n-C9F19(1b), n-C10F21(1c), n-C11F23(1d)}以及(4,4’-bis(RfCH2CH2OCH2)-2,2’-bpy)，{Rf = n-C8F17(1e) }來進行本次的實驗。而配位基1a-e除了有高含氟數也同時擁有很好的氟親和力，在FC 77/CH2Cl2溶劑系統下，配位基1a-e的分布係數分別為1：1.07, 1：1.04, 42：1, 70：1以及6.56：1。我們將金屬1a-e跟[Pd(CH3CN)2Cl2]經過簡單的攪拌便可得到新的鈀錯合物[PdCl2(4,4’-bis-(RfCH2OCH2)-2,2’-bpy)]，{Rf = n-C8F17(2a), n-C9F19(2b), n-C10F21(2c), n-C11F23(2d)}及[PdCl2(4,4’-bis-(RfCH2CH2OCH2)-2,2’-bpy)]，{Rf = n-C8F17(2e) }。新型的鈀錯合物2a-e在室溫下並不會溶解於有機溶劑，只會溶解於含氟溶劑FC 77(主要成分為C8F18)裡面。以FBS以及Thermomorphic系統下，鈀金屬錯合物2a-e在Heck反應中，可以擁有不錯的反應性以及有很好的金屬觸媒回收及再利用的效果。
關鍵字
雙吡啶並列摘要
Five highly fluorinated bipyridine derivatives, (4,4’-bis(RfCH2OCH2)-2,2’-bpy), {Rf = n-C8F17(1a), n-C9F19(1b), n-C10F21(1c), n-C11F23(1d)} and (4,4’-bis(RfCH2CH2OCH2)-2,2’-bpy), {Rf = n-C8F17(1e)} have been synthesized using 4,4’-bis(bromomethylene)¬-2,2′-bpy and fluorinated alkoxides. The ligands have high fluorine contents and also high fluorophilicity, the partition ratio being 1：1.07, 1：1.04, 42：1, 70：1 and 6.56：1 for the FC 77/CH2Cl2 system, respectively. The reactions of ligands 1a-e with [Pd(CH3CN)2Cl2] result in new palladium complexes [PdCl2(4,4’-bis-(RfCH2OCH2)-2,2’-bpy)], where{Rf = n-C8F17(2a), n-C9F19(2b), n-C10F21(2c), n-C11F23(2d)}, and [PdCl2(4,4’-bis-(RfCH2CH2OCH2)-2,2’-bpy)], where{Rf = n-C8F17(2e)} respectively. Insoluble in organic solvents at room temp, the novel Pd complexes 2a-e dissolves in fluorinated solvents only, for instance FC77, which is mainly C8F18. The Pd complexes 2a-e have been successfully tested as the generic and recyclable catalysts in Heck-type and Suzuki-type reactions under the fluorous biphasic and thermomorphic conditions.