无溶剂下钴卟啉/NHPI催化甲苯选择性氧化制备苯甲醛  

Solvent-free selective aerobic oxidation of toluene to benzaldehyde catalyzed by cobalt porphyrin/NHPI

作　　者：贺晓琪 钟思奇 林亚松 周贤太 He Xiaoqi;Zhong Siqi;Lin Yasong;Zhou Xiantai(Huizhou Research Institute,Sun Yat-sen University,Huizhou 516081,Guangdong,China;School of Chemical Engineering and Technology,Sun Yat-sen University,Zhuhai 519082,Guangdong,China)

机构地区：[1]中山大学惠州研究院,广东惠州5106081 [2]中山大学化学工程与技术学院,广东珠海519082

出　　处：《工业催化》2023年第10期69-74,共6页Industrial Catalysis

基　　金：国家自然科学基金资助项目(22278451,21938001);广东省基础与应用基础研究基金项目(2019A1515110979,2022B1515120057)。

摘　　要：以钴卟啉/N-羟基邻苯二甲酰亚胺(NHPI)为催化剂,分子氧为氧化剂,在无溶剂的条件下,研究温和条件下催化甲苯选择性氧化制备苯甲醛的工艺。在甲苯0.2 mol、钴卟啉物质的量分数1×10^(-4)%、NHPI物质的量分数0.25%、70℃、O_(2)压力2.0 MPa和3 h优化条件下,甲苯转化率为5.5%,苯甲醛、苯甲醇和苯甲酸选择性分别为88.0%、10.2%和0.8%。通过原位红外和电子顺磁共振波谱仪等表征方法,表明该反应机理为典型的自由基反应过程。Solvent-free protocol for the selective aerobic oxidation of toluene to benzaldehyde catalyzed by cobalt porphyrin/N-hydroxy phthalimide(NHPI)under mild conditions was developed.Under the optimized conditions(toluene 0.2 mol,molar fraction of cobalt porphyrin 10x0E䥺SymboltB@0x0F10-4%,molar fraction of NHPI 0.25%,70℃,O_(2)pressure 2.0 MPa,3 h),the conversion of toluene was 5.5%,and the selectivity of benzaldehyde,benzyl alcohol,and benzoic acid was 88.0%,10.2%,and 0.8%,respectively.Based on in situ characterizations such as infrared spectroscopy and electron paramagnetic resonance spectroscopy,the reaction mechanism involved free radicals was demonstrated.

关 键 词：有机化学工程 甲苯 氧化 苯甲醛 选择性 无溶剂 

分 类 号：TQ244.1[化学工程—有机化工] TQ426.94