金属卟啉类仿生催化剂的合成、构效关系及在催化氧化碳氢化合物中的应用  

Synthesis and QSAR of Metal Porphyrin Biomimetic Catalysts and Their Application in Oxidation of Hydrocarbons

作　　者：佘远斌[1] 王兰芝[1] 宋旭锋[1] 张燕慧[1] 陈一霞[1] 

机构地区：[1]北京工业大学化学化工系绿色化学与药物合成研究所,北京100022

出　　处：《精细化工》2005年第6期401-408,共8页Fine Chemicals

基　　金：国家自然科学基金重点项目(批准号:20436010);北京市自然科学基金项目(批准号:2002002);北京市科技新星计划项目(批准号:953811200);国家教育部优秀青年骨干教师资助计划项目;大连理工大学精细化工国家重点实验室开放基金的经费资助。~~

摘　　要：综述了金属卟啉类仿生催化剂的理论基础、合成、构效关系及其在仿生催化氧化烃类绿色合成有机中间体和产品方面的研究进展。重点报道了该课题组和郭灿城课题组近年来在金属卟啉类仿生催化剂的分子设计、合成方法、构效关系及其在催化空(氧)气选择氧化各种芳烃侧链、环烷烃绿色合成芳醛、芳酸、环己酮、己二酸等重要有机中间体及精细化学品方面的研究成果,特别是由湖南大学郭灿城教授与中石化联合开发的完全拥有我国知识产权的仿生催化空气氧化环己烷(80～140℃,0.5～0.8MPa下反应2h)制取环己醇及环己酮的新技术,已于2003年首次成功地实现了产业化,其中,环己烷的转化率可达8%～10%,环己醇及环己酮的选择性可达90%。最后,对仿生催化技术的发展方向及应用前景进行了展望。引用文献57篇。Research progress on the theoretical background,synthesis and QSAR of metal porphyrin biomimetic catalysts and their application in green synthesis of organic intermediates and products by oxidation of hydrocarbons are reviewed.The research achievements on metal porphyrin biomimetic catalysis of our group and professor Guo Cancheng′ group in recent years are systematically and emphatically reported,including design,synthesis and QSAR of metal porphyrin and metal phthalocyanine biomimetic catalysts and their application in green synthesis of o,m,p-nitrobenzoic acids,o,p-nitro-benaldehydes,adipic acid,cyclohexanone,cyclohexanol,dihydroxybenzenes etc. by catalytic oxidation of o,m,p-nitrotoluenes,cyclohexane,phenol and other hydrocarbons.The most importment achievement was that the novel technology of catalytic oxidation of cyclohexane to cyclohexanone and cyclohexanol with μ-oxo-bisironporphyrin compounds as biomimetic catalysts and air as oxidant at 80～140 ℃,0.5～0.8 MPa for 2 h,joint-developed by Professor Guo Cancheng in Hunan University and SINOPIC and possessing complete knowledge property (patents) of our country,was industrialized successfully for the first time in 2003.The conversion of cyclohexane reached 8%～10% and selectivity for cyclohexanone and cyclohexanol reached 90%.In addition, the novel process for preparing o,p-nitrobenzoic acids by liquid-phase oxidation of o,p-nitrotoluenes with biomimetic catalysts metal phthalocyanines and porphyrins in the presence of dioxygen was investigated;yield of o-nitrobenzoic acid about 79% and yield of p-nitrobenzoic acid about 90% were achieved.Finally,the tendency and prospect of biomimetic catalytic oxidation of hydrocarbons are introduced briefly.57 refrences are cited

关 键 词：金属卟啉 仿生催化 烃类氧化 绿色合成 

分 类 号：TQ426.8[化学工程]