可回收性NS-MCM-41-Pd催化有機鋅試劑之醯化反應

在許多有機反應中，以過渡金屬作為催化劑之合成已成為趨勢，而非均相鈀觸媒更是被廣泛使用之觸媒，因其具有良好之催化效能且擁有可回收再使用之特性。我們選擇以中孔洞矽材nanosized MCM-41 (NS-MCM-41) 做為擔體，利用後修飾法將含bipyridine配位基之鈀金屬錯合物嫁接於孔道內部，合成出可回收使用之固態觸媒NS-MCM-41-Pd，目前已成功應用於Heck reaction、Sonogashira reaction、Kumada reaction等偶合反應。　　為延伸NS-MCM-41-Pd之應用性，我們利用此觸媒系統來催化有機鋅試劑 (烷基、芳香族及炔基) 與各種不同醯氯 (acyl chlorides) 之偶合反應，大部分反應皆可於溫和之條件下得到高產率。而固體之NS-MCM-41-Pd催化劑亦具有回收再使用之性質。反應之混合物經由離心將溶液去除後，固體部分再以稀鹽酸及有機溶劑沖洗數次，即可進行下一次反應。研究顯示回收後之固態NS-MCM-41-Pd觸媒可回收利用至少五次。

關鍵字

鈀金屬錯合物； nanosized MCM-41 ；有機鋅試劑

並列摘要

Palladium bipyridyl complex anchored inside the channels of nanosized MCM-41 was found to be an efficient and powerful catalyst for various organic coupling reactions. By the catalysis of NS-MCM-41-Pd, many cross-coupling process such as the Heck reaction, Sonogashira reaction, Kumada reaction, etc. were accomplished. We are also investigating more and more coupling reactions nowadays. In order to extend the scope of NS-MCM-41-Pd catalyst, we proceeded to test the coupling reaction between organozinc reagents (alkyl, aryl, and alkynyl) and variety of acyl chlorides by means of the NS-MCM-41-Pd catalyst. Most reactions could be conducted under mild conditions. (All reactions were carried out at 50oC in THF, under N2). NS-MCM-41-Pd catalyst is also recyclable. Solid catalyst could be separated from reaction mixtures by centrifugation and washing with HCl/H2O and organic solvent. We found that the recycled catalyst could be reused at least 5 times.

並列關鍵字

Palladium bipyridyl complex ； nanosized MCM-41 ； organozinc reagents

參考文獻

[1] J. W. McBain, The Sorption of Gases and Vapours by Solids, Rutledge and Sons, London, ch. 5, 1932.

[6] P. M. Price, J. H. Clark, D. J. Macquarrie, J. Chem. Soc., Dalton Trans. 2000, 101.

[12] A. Sayari, J. of Phys. Chem. B 1998, 102, 5503.

[16] C. P. Mehnert, D. W. Weaver, J. Y. Ying, J. Am. Chem. Soc. 1998, 120, 12289

[17] W. Hao, J. Sha, S. Sheng, M. Cai, J. Mol. Catal. A 2009, 298, 94

國際替代計量

可回收性NS-MCM-41-Pd催化有機鋅試劑之醯化反應

未授權

主題瀏覽