氮杂冠醚取代单Schiff碱过渡金属配合物催化氧化对二甲苯研究  

Study on catalytic oxidation for p-xylene to p-toluic acid by mono-Schiff base complexes with pendant aza-crown ether

作　　者：王涛[1] 李建章[1] 魏磊[1] 胡伟[1] 程杰[1] 向珍[1] 

机构地区：[1]绿色催化四川省高校重点实验室/四川理工学院化学与制药工程学院,四川自贡643000

出　　处：《化学研究与应用》2012年第7期1125-1129,共5页Chemical Research and Application

基　　金：四川省教育厅重点专项项目(2005D007)资助;绿色催化四川省高校重点实验室项目(LZJ01;LZJ1101)资助;自贡市科技局项目(10X01)资助

摘　　要：本文将苯并-10-氮杂-15-冠-5或吗啉基取代的单Schiff碱过渡配合物作为催化剂,在常压和120℃条件下,以空气为氧源,研究了对二甲苯催化氧化反应。实验探讨了Schiff碱配合物中心金属离子、Schiff碱配体中挂接的氮杂冠醚环、配体芳环上取代基和反应时间等对对二甲苯催化氧化反应的影响。实验结果表明:Schiff碱配合物中氮杂冠醚的存在能显著缩短反应诱导期,提高催化反应活性和产物选择性;Schiff碱Mn(III)配合物比Schiff碱Co(II)具有更高的催化反应活性;氮杂冠醚Schiff碱Mn(III)配合物对于二甲苯的催化氧化反应转化率大于60%,对甲苯甲酸产物的选择性均高于70%。mono-Schiff base complexes with pendant aza-crown or morpholino groups had been studied as catalysts in aerobic oxidation of p-xylene to p-toluic acid（PTA）with air at 120℃ under normal atmospheric pressure.The effects of central metal of Schiff base complexes,the aza-crown ether group pendant and the substituents group in Schiff base ligands and the reaction time on the oxidation of p-xylene were also investigated.The results revealed that the catalytic activity of mono-Schiff base complexes binding aza-crown ether pendants could be visibly improved and the induce period of the oxidation for p-xylene to p-toluic acid was shortened.Schiff base manganese（III）complexes had higher catalytic activity than cobalt（II）complexes under the same ligand.Significant selectivity（up to～70%）and conversion levels（up to～60%）were obtained in the presence of aza-crown ether substituted mono-Schiff base Mn（III）complexes.

关 键 词：氮杂冠醚 单Schiff碱 过渡金属配合物 对二甲苯氧化 催化氧化 

分 类 号：O614.81[理学—无机化学]