Aerobic oxidation of cyclohexene catalyzed by Fe(III)(5,10,15,20-tetrakis(pentafluorophenyl)porphyrin)Cl in supercritical CO2

被引:10
作者
Kokubo, Y
Wu, XW
Oshima, Y
Koda, S
机构
[1] Sophia Univ, Fac Sci & Technol, Dept Chem, Chiyoda Ku, Tokyo 1028554, Japan
[2] Univ Tokyo, Sch Engn, Dept Chem Syst Engn, Bunkyo Ku, Tokyo 1138656, Japan
基金
日本学术振兴会;
关键词
aerobic oxidation; iron porphyrins; cyclohexene; supercritical CO2; radical chain reaction;
D O I
10.1016/S0896-8446(03)00168-2
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
The kinetics of aerobic oxidation of cyclohexene catalyzed by Fe(III)(5,10,15,20-tetrakis(pentafluorophenyl)porphyrin)Cl in supercritical CO2 was studied at 50 degreesC and 165 atm of the total pressure with ca. 20 atm O-2 partial pressure. The reaction proceeded to yield allylic oxidation products, i.e. 2-cyclohexen-1-ol and 2-cyclohexen-1-one, and epoxidation products, i.e. cyclohexene oxide and 7-oxabicyclo[4,1,0]heptan-2-one. The reaction was retarded in the presence of radical inhibitor, 2,6-di-tert-butyl-4-methylphenol. The overall reaction rate under the steady state was dependent with ca. second order on the cyclohexene concentration, and zero order on the O-2 concentration except for the very small O-2 pressure range. These kinetic behaviors could be analyzed on the basis of the free radical allylic oxidation mechanism. (C) 2003 Elsevier B.V. All rights reserved.
引用
收藏
页码:225 / 235
页数:11
相关论文
共 11 条
[1]   Metalloporphyrin-catalyzed homogeneous oxidation in supercritical carbon dioxide [J].
Birnbaum, ER ;
Le Lacheur, RM ;
Horton, AC ;
Tumas, W .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1999, 139 (01) :11-24
[2]  
BIRNBAUM ER, 1995, J MOL CATAL A-CHEM, V104, P119
[3]  
BOETTCHER A, 1997, J MOL CATAL A-CHEM, V117, P229
[4]   Significant electronic effect of porphyrin ligand on the reactivities of high-valent iron(IV) oxo porphyrin cation radical complexes [J].
Goh, YM ;
Nam, WW .
INORGANIC CHEMISTRY, 1999, 38 (05) :914-920
[5]   Homogeneous catalysis in supercritical fluids [J].
Jessop, PG ;
Ikariya, T ;
Noyori, R .
CHEMICAL REVIEWS, 1999, 99 (02) :475-493
[6]   METALLOPORPHYRIN-CATALYZED OXIDATION OF ALKANES WITH MOLECULAR-OXYGEN IN THE PRESENCE OF ACETALDEHYDE [J].
MURAHASHI, SI ;
NAOTA, T ;
KOMIYA, N .
TETRAHEDRON LETTERS, 1995, 36 (44) :8059-8062
[7]   Olefin epoxidations using supercritical carbon dioxide and hydrogen peroxide without added metallic catalysts or peroxy acids [J].
Nolen, SA ;
Lu, J ;
Brown, JS ;
Pollet, P ;
Eason, BC ;
Griffith, KN ;
Gläser, R ;
Bush, D ;
Lamb, DR ;
Liotta, CL ;
Eckert, CA ;
Thiele, GF ;
Bartels, KA .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 2002, 41 (03) :316-323
[8]   Cytochrome P-450 model reactions: a kinetic study of epoxidation of alkenes by iron phthalocyanine [J].
Safari, N ;
Bahadoran, F .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2001, 171 (1-2) :115-121
[9]   Dioxygen activation by iron complexes. The search for reactive intermediates [J].
Selke, M ;
Sisemore, MF ;
Ho, RYN ;
Wertz, DL ;
Valentine, JS .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1997, 117 (1-3) :71-82
[10]   MODEL REACTIONS RELATED TO CYTOCHROME-P-450 - EFFECTS OF ALKENE STRUCTURE ON THE RATES OF EPOXIDE FORMATION [J].
TRAYLOR, TG ;
XU, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (06) :1953-1958