高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (10): 2311.

• 研究论文 • 上一篇    下一篇

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

崔巧利,  徐士超,  孙呈郭,  胡炳成   

  1. 南京理工大学化工学院, 南京210094
  • 收稿日期:2010-10-20 修回日期:2010-11-30 出版日期:2011-10-10 发布日期:2011-09-11
  • 通讯作者: 胡炳成 E-mail:hubingcheng@yahoo.com
  • 基金资助:

    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.

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

CUI Qiao-Li, XU Shi-Chao, SUN Cheng-Guo, HU Bing-Cheng*   

  1. School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
  • Received:2010-10-20 Revised:2010-11-30 Online:2011-10-10 Published:2011-09-11
  • Contact: HU Bing-Cheng E-mail:hubingcheng@yahoo.com
  • Supported by:

    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%.

关键词: 氯化血红素, 卟啉衍生物; , 催化氧化, 机理

Abstract: 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%.

Key words: Hemin, Porphyrin derivative, Catalytic oxidation, Mechanism

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