次卟啉二甲酯钴络合物均相选择性催化氧化环己烷  

Selective Oxidation of Cyclohexane Catalyzed by Metallo-Deuteroporphyrins in Homogeneous Solution

作　　者：周维友[1] 胡炳成[1] 刘祖亮[1] 

机构地区：[1]南京理工大学化工学院,南京210094

出　　处：《应用化学》2010年第4期424-427,共4页Chinese Journal of Applied Chemistry

基　　金：江苏省自然科学基金(BK2009386);南京理工大学科技发展基金(XKF09008)资助项目

摘　　要：以次卟啉二甲酯钴[Co(DPDME)]为仿生催化剂,分子氧(空气)为氧给体,无其它辅助催化剂的条件下研究了催化氧化环己烷的反应。考察了反应温度、空气压力、催化剂用量和卟啉配体结构对醇酮的产率及选择性的影响。结果表明,在相同条件下,次卟啉二甲酯钴的催化活性明显高于其它的钴卟啉催化剂。以次卟啉合钴为催化剂,浓度为0.015 mmol/L,反应温度423 K,在空气压强为0.8 MPa的条件下反应5 h,环己烷的转化率达到18.2%,选择性为87.4%。温度对次卟啉钴的催化活性影响较大,温度高于443 K时,催化剂的稳定性降低,但是其转化数仍达到了66 646。对次卟啉二甲酯钴催化空气氧化环己烷的反应路径作了初步探讨。To search for the efficient biomimetic catalysts for the oxidation of hydrocarbon,cobalt deuteroporphyrin [Co（DPDME）] was used as catalyst for the oxidation of cyclohexane with air.The effects of reaction temperature,pressure of air,the catalyst amount and different complexes were evaluated.The experiment results show that Co（DPDME） is more effective than the others,and the optimum reaction conditions for the oxidation of cyclohexane are：c=0.015 mmol/L,reaction temperature 423 K,pressure of air 0.8 MPa,reaction time 5 h.Under the optimum conditions,the conversion rate of cyclohexane could reaches to 18.2%,the total selectivity of cyclohexanol and cyclohexanone is 87.4%.The temperature has much more influence on the catalytic reaction.Although the stability of Co（DPDME） was reduced when the temperature is higher than 443 K,the turnover number reaches 66 646.We also discussed the possible reaction path of Co（DPDME）-catalyzed oxidation of cyclohexane with oxygen.

关 键 词：金属次卟啉 环己烷 选择氧化 

分 类 号：O621.2[理学—有机化学]