Effective catalysis of simple metalloporphyrins for cyclohexane oxidation with air in the absence of additives and solvents

被引:151
作者
Guo, CC [1 ]
Chu, MF [1 ]
Liu, Q [1 ]
Liu, Y [1 ]
Guo, DC [1 ]
Liu, XQ [1 ]
机构
[1] Hunan Univ, Coll Chem & Chem Engn, Changsha 410082, Peoples R China
基金
中国国家自然科学基金;
关键词
metalloporphyrins; cyclohexane oxidation; air; catalysis;
D O I
10.1016/S0926-860X(03)00061-9
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Simple iron, manganese and cobalt tetraphenylporphyrins were synthesized and used to catalyze cyclohexane oxidation with air in the absence of additives and solvents. These simple metalloporphyrins were first found to be the very effective catalysts for cyclohexane oxidation with air when the reaction temperature was higher than 100 degreesC and pressure was greater than 0.4 MPa. The research results showed that the metal loporphyrins type, temperature, pressure and catalyst concentration influenced the yields and conversion of cyclohexane oxidation with air. The catalytic activity of cobalt porphyrins was superior to that of iron and manganese porphyrins. For cyclohexane oxidation catalyzed by simple cobalt tetrapherylporphyrin, the conversion of cyclohexane was up to 16.2%, general yields of cyclohexanol and cyclohexanone was 82%, and the mole turnover numbers of the catalyst reached 400,000 under the optimum conditions of 0.6 MPa and 140 degreesC and 4 ppm cobalt porphyrin. (C) 2003 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:303 / 309
页数:7
相关论文
共 47 条
[1]  
ANATOLI O, 1973, J ORG CHEM, V38, P3729
[2]  
[Anonymous], 1994, METALLOPORPHYRINS CA
[3]  
[Anonymous], CHIN J ORG CHEM
[4]   SYNTHESIS AND REMARKABLE PROPERTIES OF IRON BETA-POLYNITROPORPHYRINS AS CATALYSTS FOR MONOOXYGENATION REACTIONS [J].
BARTOLI, JF ;
BATTIONI, P ;
DEFOOR, WR ;
MANSUY, D .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1994, (01) :23-24
[5]   THE FUNCTIONALIZATION OF SATURATED-HYDROCARBONS .19. APPLICATION OF TERT-BUTYL HYDROPEROXIDE AND DIOXYGEN USING SOLUBLE FE(III) AND CU(II) CHELATES [J].
BARTON, DHR ;
BEVIERE, SD ;
HILL, DR .
TETRAHEDRON, 1994, 50 (09) :2665-2670
[6]  
BOWNY VW, 1991, BIOCHEM BIOPH RES CO, V113, P5699
[7]   Multiple active oxidants in cytochrome P-450 model oxidations [J].
Collman, JP ;
Chien, AS ;
Eberspacher, TA ;
Brauman, JI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (45) :11098-11100
[8]   Oxidation of alkanes and alkenes by iodosylbenzene and hydrogen peroxide catalysed by halogenated manganese porphyrins in homogeneous solution and covalently bound to silica [J].
Doro, FG ;
Smith, JRL ;
Ferreira, AG ;
Assis, MD .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2000, 164 (1-2) :97-108
[9]  
GOULD DG, 1976, J ORG CHEM, V42, P1
[10]   MECHANISM OF CATALYTIC OXYGENATION OF ALKANES BY HALOGENATED IRON PORPHYRINS [J].
GRINSTAFF, MW ;
HILL, MG ;
LABINGER, JA ;
GRAY, HB .
SCIENCE, 1994, 264 (5163) :1311-1313