利用NS-MCM-41-Pd催化醯氯與末端炔及三苯基鉍反應形成有機炔酮及酮類之反應

Coupling reactions of acyl chlorides with terminal alkynes and triarylbismuths catalyzed by NS-MCM-41-Pd to produce ynones and ketones

陳俊友(Jun-You Chen)

指導教授 ： 蔡福裕

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2008年)

https://doi.org/10.6841/NTUT.2008.00572

摘要

本研究是利用非均相催化劑來進行有機合成的反應，我們實驗室以大小約70-120 nm的中孔洞二氧化矽材料，NS-MCM-41做為無機擔體，此類的中孔洞沸石其孔洞為蟲洞結構(wormhole-like)，通道間互通性良好，反應物和產物易在通道間進出，能增進反應系統的分散性。並且高熱穩定性質，高表面積(約705 m2/g)，表面上有大量的silanol group，因此我們以後修飾法將含bipyridine配位基之鈀金屬錯合物架接在孔璧上，合成出固相的觸媒NS-MCM-41-Pd來催化醯氯與末端炔反應形成有機炔酮以及醯氯與三苯基鉍形成酮類的反應。其非均相催化反應的能力可逼近均相催化反應。反應結束後，用簡單的離心方式將觸媒回收再使用，重複循環於下一次的反應，且NS-MCM-41與鈀金屬錯合物是以共價鍵形式結合而成，可有效降低反應時鈀金屬之流失，在反應重複進行時，其再回收使用催化反應的能力極佳。

關鍵字

非均相催化劑 ； NS-MCM-41 ； 中孔洞材料 ； 鈀金屬錯合物

並列摘要

Chemists have demonstrated the organic synthesis in a variety of palladium complex as a homogeneous catalyst which in contrast to heterogeneous catalyst, often difficult to be separated from the reaction mixtures. Nanosized mesoporous silica, NS-MCM-41, is a useful support to be a heterogeneous catalyst. There are several advantages of NS-MCM-41: (1) thermally stable, (2) wormhole-like mesostructure for the exchange of reactants and products (3) large surface area and Silanol groups for surface modification. Accordingly, our group developed a heterogeneous catalyst, NS-MCM-41-Pd, in which palladium bipyridyl complex is immobilized into NS-MCM-41, and NS-MCM-4-Pd is an efficient and re-usable catalyst on coupling reactions.
A palladium bipyridyl complex anchored onto nanosized MCM-41 was as a catalyst to carry out the coupling of acyl chlorides and triarylbismuths for the formation of diaryl ketones and arylcyclehexyl ketones。NS-MCM-41-Pd was also work well in the formation of ynones by the reaction of acyl chlorides with terminal alkynes. The catalyst can be recovered by centrifugation and recycled several times only slightly decreasing its activity. Hot filtration of the reaction mixture under N2 indicated only slightly lost of the metal in the solution.

並列關鍵字

heterogeneous catalyst ； NS-MCM-41 ； mesoporous material ； palladium complex

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