Co(Ⅱ)-3,8-双乙基次卟啉二甲酯的合成及催化空气氧化环己烷应用  

Synthesis and Catalytic Application of Co(Ⅱ)-3,8-diethyl Deuteroporphyrin Dimethyl Ester to the Oxidation of Cyclohexane

作　　者：崔巧利[1] 徐士超[1] 孙呈郭[1] 胡炳成[1] 

机构地区：[1]南京理工大学化工学院,南京210094

出　　处：《高等学校化学学报》2011年第10期2311-2315,共5页Chemical Journal of Chinese Universities

基　　金：江苏省自然科学基金(批准号:BK2009386);南京理工大学科技发展基金(批准号:XKF09008)和南京理工大学自主科研专项计划项目(批准号:2010GJPY043)资助

摘　　要：以氯化血红素为原料,经过脱铁、酯化、催化加氢和络合金属得到仿生催化剂Co(Ⅱ)-3,8-二乙基次卟啉二甲酯.在无其它外加溶剂及共还原剂的条件下,将其应用到催化空气氧化环己烷反应,将实验结果同Co(Ⅱ)原卟啉二甲酯催化氧化空气氧化环己烷的结果进行对照,并对催化氧化的机理进行了初步研究.实验结果表明,Co(Ⅱ)-3,8-双乙基次卟啉二甲酯克服了Co(Ⅱ)原卟啉二甲酯3,8-位乙烯基取代基不稳定的缺点,能够很好催化空气氧化环己烷,环己醇和环己酮的总收率达16.9%.The oxidation of alkane,alkene and carbonyl catalyzed by metallo-deuteroporphyrin derivatives were reviewed.Because of their closer relationship to monooxygenase P-450,metallo-deuteroporphyrin derivatives have higher catalytic activities than other metallo-porphyrin derivates.The Co（Ⅱ）-3,8-diethyl deuteroporphyrin dimethyl ester was prepared from hemin by a four-steps reaction including demetalation,esterification,hydrogenation and complex reactions.Without the additional of organic solven and any coreductant,Co（Ⅱ）-3,8-diethyl deuteroporphyrin dimethyl ester was used as catalyst for cyclohexane oxidation using air as oxidant.The catalytic mechanism of this reaction was preliminary studied by UV-Vis spectra.The results indicated that the Co（Ⅱ）-3,8-diethyl deuteroporphyrin dimethyl ester which overcame the shortage of instabili-ties of 3,8-divinyl of cobalt（Ⅱ） protoporphyrin IX dimethyl ester had satisfying catalytic activity in the oxidation of cyclohexane and the total yield of cyclohexanol and cyclohexanone was 16.9%.

关 键 词：氯化血红素 卟啉衍生物 催化氧化 机理 

分 类 号：O626[理学—有机化学]