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单金属锰、铁卟啉对空气氧化α-蒎烯的催化作用及取代基效应
引用本文:段晓惠,何荣幸,李象远,罗春燕.单金属锰、铁卟啉对空气氧化α-蒎烯的催化作用及取代基效应[J].高等学校化学学报,2005,26(9):1690-1694.
作者姓名:段晓惠  何荣幸  李象远  罗春燕
作者单位:四川大学化工学院,成都,610065
基金项目:国家自然科学基金;教育部科学技术研究项目
摘    要:以α-蒎烯为底物,空气作氧化剂,研究了苯环上带有不同取代基团的单锰卟啉和单铁卟啉对空气氧化α-蒎烯的催化作用及反应中的取代基效应.结果表明,单锰卟啉及单铁卟啉催化氧化α-蒎烯得到双键和烯丙位一、二级碳氢键的氧化产物,没有烯丙位三级碳氢键的氧化产物.环氧化合物是主要产物,而且氧化产物的产率随时间的变化呈较好的线性关系.随着苯环上meso位取代基Cl,CH3,OCH3和OH的供电子能力的增强,锰卟啉和铁卟啉对α-蒎烯的催化活性逐渐减弱,α-蒎烯的转化率逐渐降低.锰卟啉和铁卟啉的催化反应表观速率常数k与环外苯基上的取代基特性常数σ均呈良好的线性关系,Hammett关系式分别为lnk=1.2168σ-7.9968,lnk=0.6251σ-8.2426;线性相关系数分别为0.9507和0.9715.

关 键 词:α-蒎烯  金属卟啉  催化  氧化  取代基效应
文章编号:0251-0790(2005)09-1690-05
收稿时间:08 16 2004 12:00AM
修稿时间:2004-08-16

Theoretical Investigation of Structure and Electronic Spectrum of Benzil
DUAN Xiao-Hui,HE Rong-Xing,LI Xiang-Yuan,LUO Chun-Yan.Theoretical Investigation of Structure and Electronic Spectrum of Benzil[J].Chemical Research In Chinese Universities,2005,26(9):1690-1694.
Authors:DUAN Xiao-Hui  HE Rong-Xing  LI Xiang-Yuan  LUO Chun-Yan
Institution:College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
Abstract:Catalysis and substituent effects of monomanganese-porphyrins and monoiron-porphyrins with different substituents on the phenyl rings for α-pinene oxidation with air were studied. The results showed that the product mixture was composed of components resulting from the oxidation of C=Cbond and allylic secondary and primary C-H bonds in α-pinene. No oxidation products of allylic tertiary C-H bond were detected. the main component of the product mixture was α-pinene oxide. The yields of various oxidation products increased linearly with the increase of the reaction time when α-pinene oxidation was catalyzed by the experimental mentallo-porphyrins. With increasing the electron-donating abilities of the substituents on the meso sites of phenyl rings of monomanganese-porphyrins and monoiron-porphyrins, their catalytic activities was weakened and the conversions of α-pinene decreased. There were linear relationships between the reaction kinetic constant k and the substituent constant σ of the two kinds of metallo-porphyrins, and the Hammett equations: lnk=1.2168σ-7.9968 for monomanganese-porphyrins and lnk=0.6251σ-8.2426 for monoiron-porphyrins. The linear coefficients were 0.950 7 and 0.971 5, respectively.
Keywords:Excitation state  Absorption and emission spectra  Solvent effects  Stocks shift
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