金属卟啉仿生催化绿色合成对硝基苯甲醛的新方法  

NOVEL TECHNOLOGY FOR GREEN SYNTHESIS OF p-NITROBENZALDEHYDE WITH METALLOPORPHYRINS AS BIOMIMETIC CATALYSTS

作　　者：佘远斌[1] 范莉莉[1] 张燕慧[2] 宋旭锋[1] 

机构地区：[1]北京工业大学环境与能源工程学院绿色化学研究室,北京100022 [2]北京工业大学生命科学与生物工程学院,北京100022

出　　处：《化工学报》2004年第12期2032-2037,共6页CIESC Journal

基　　金：国家教育部优秀青年骨干教师资助项目(No200202-00);北京市自然科学基金(No2002002);大连理工大学精细化工国家重点实验室开放基金资助项目~~

摘　　要：对硝基苯甲醛是应用非常广泛的重要精细有机化工中间体 .针对目前对硝基苯甲醛生产方法中存在的问题 ,采用金属卟啉类仿生催化剂代替常规催化剂 ,以清洁廉价的氧气 /空气代替环境污染严重的化学氧化剂 ,以甲醇 碱性介质代替设备腐蚀严重的酸性介质 ,研究了一种能在 30～ 5 0℃、 0 5～ 2 0MPa、反应 6～ 12h的温和条件下 ,催化氧气液相氧化对硝基甲苯绿色合成对硝基苯甲醛的新方法 .研究结果表明 :在优化条件下及T(o Cl)PPMn催化剂 :6 0× 10 -5mol·L-1;NaOH浓度 :1 8mol·L-1;4 5℃、 1 6MPa反应 10h下 ,对硝基甲苯的单程转化率可达到 83 0 % ,对硝基苯甲醛的选择性和收率分别可达 87 9%和 73 0 % .p-Nitrobenzaldehyde, an important intermediate for the manufacture of fine chemicals, was widely used for the preparation of pharmaceutical drugs, dyes, pesticides and non-linear optic materials. p-Nitrobenzaldehyde was prepared indirectly in industrial scale via p-nitrotoluene with chemical oxidants such as potassium permanganate or nitric acid. However such problems as severe environmental pollution, equipment corrosion, and large energy consumption remain to be solved. A novel technology for green synthesis of p-nitrobenzaldehyde by dioxygen oxidation of p-nitrotoluene under mild conditions of 30-50°C, 0.5-2.0 MPa for 6-12 h was investigated in order to solve above problems. The novel technology was characterized by metalloporphyrin biomimetic catalysts to replace conventional catalysts, with clean oxygen/air replacing chemical oxidants polluting environment, and methanol-NaOH alkali medium replacing corrosive acidic medium. The effects of the center metal ions, substituents and their position, and ligands in axis of catalysts and reaction time on the conversion of p-nitrotoluene, selectivity and yield of p-nitrobenzaldehyde were investigated systematically. The results showed that the conversion of p-nitrotoluene was up to 83.0%, and the maximum selectivity and yield of p-nitrobenzaldehyde were 87.9% and 73.0% respectively under the optimum conditions: methanol as solvent, 1.8 mol &middot L-1 of NaOH concentration, 6.0 × 10-5 mol &middot L-1 of T (o-Cl) PPMn catalyst, reaction at 45°C, 1.6 MPa for 10 h.

关 键 词：对硝基苯甲醛 合成新方法 金属卟啉 仿生催化 氧气氧化 对硝基甲苯 

分 类 号：O643.6[理学—物理化学] TQ245.1[理学—化学]