以陽離子型含氟鏈(η3丙烯基)鈀錯合物在溫控系統下(或在微波反應器裡)進行Mizoroki-Heck反應

Cationic(η3-Allyl) Palladium Complexes Bearing Fluoro-ponytailed Bipyridine ligands-catalyzed Mizoroki-Heck Reaction under Thermomorphic Mode(or in Microwave Reactor)

李杰耕(Chieh-Keng Li)

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(2010年)

摘要

將含氟鏈聯吡啶螯合劑[4,4′-bis(RfCH2OCH2)-2,2′-bpy，1a-c，Rf= C9F19 (a)，C10F21 (b)，C11F23 (c)] 加入Allylpalladium(II) chloride dimer和AgOTf (OTf= CF3SO3)來合成陽離子型含氟鏈(η3-丙烯基)鈀錯合物 {[Pd(η3-allyl)(4,4′-bis-(RfCH2OCH2)-2,2′-bpy)](OTf)，2a-c}，當溫度在10~45℃時，2a-c對極性有機溶劑有較顯著的溶解度，但是溫度在－20~－30℃時則不溶，所以證明2a-c可以在溫控系統下進行Heck反應並且在反應完後再使用，以2b做為觸媒時，用aryl bromide和methyl acrylate以DMF做為溶劑在150℃下進行Heck反應，每次反應大約在15個小時，反應結束後冷卻至－20℃，然後讓觸媒沉澱後再次使用，回收產物後利用GC-MS進行鑑定，產率大約為90~100%，以iodobenzene和methyl acrylate最多總共可以反應十五次。

關鍵字

海克反應 ； 催化 ； 溫控系統

並列摘要

The reaction of allylpalladium(II) chloride dimer and [4,4′-bis(RfCH2OCH2)-2,2′-bpy, 1a-c, Rf= C9F19 (a), C10F21 (b), C11F23 (c)] in the presence of AgOTf (OTf= CF3SO3) resulted in cationic complexes, [Pd(η3-allyl)(4,4′-bis-(RfCH2OCH2)-2,2′-bpy)](OTf), 2a-c, respectively. Complexes 2a-c, obvious soluble in polar organic solvents at 10~45℃but insoluble at －20~－30℃, were demonstrated as catalysts in the cationic Pd-catalyzed Heck reaction under the thermomorphic mode and recovered for reusage.
The cationic Pd-catalyzed Heck arylation of methyl acrylate with aryl bromides was selected to demonstrate the feasibility of recycling usage with 2b as the catalyst using DMF as the solvent at 150℃ for about 15 h in each run. At the end of each cycle, the product mixtures were cooled to －20℃; then catalysts were recovered by decantation. The products were quantified by GC analysis and yield was about 90~100% . The Heck reaction of C6H5I with methyl acrylate could be catalyzed by 2b with good recycling results for a total of 15 times.

並列關鍵字

Heck reaction ； catalysis ； thermomorphic mode

參考文獻

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