Oxidation and epoxidation of hydrocarbons with O-2 catalysed by EuCl3

被引:16
作者
Yamanaka, I
Akimoto, T
Nakagaki, K
Otsuka, K
机构
[1] Department of Chemical Engineering, Tokyo Institute of Technology, Ookayama Meguro-ku
关键词
europium; epoxidation; oxidation; rare earth; monooxygenation;
D O I
10.1016/1381-1169(96)00066-0
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
Oxidation of cyclohexane and epoxidation of 1-hexene with O-2 by EuCl3 catalytic systems (EuCl3, Zn powder, carboxylic acid, and solvent) were studied in detail. Combination of proton donors and solvents strongly affected the turnover number (TON) and the selectivity of the monooxygenation. The maximum TON of 11.7 in 1 h for oxidation of cyclohexane to cyclohexanol and cyclohexanone (approximate to 100% total selectivity) was obtained using acetic acid and dichloromethane at P(O-2) = 101 kPa and T = 40 degrees C. The selectivity to cyclohexanone increased with increasing the yield for sum of the products. A successive reaction of cyclohexanol to cyclohexanone became obvious at higher yields in oxidation of cyclohexane. In the case of epoxidation, the maximum TON of the epoxide (81.4% selectivity) of 14.2 in 1 h was obtained using 1,2-dichloroethane and propionic acid at P(O-2) = 101 kPa and T = 40 degrees C. The selectivity to the epoxide did not change with the total yield. A successive reaction of 1,2-epoxyhexane to by-products was not observed in the oxidation of 1-hexene. A small amount of CO2 was produced from carboxylic acid, but none from the reactant. The efficiency of Zn powder used to the monooxygenations was not more than 5%.
引用
收藏
页码:119 / 128
页数:10
相关论文
共 14 条
[1]   THE SELECTIVE FUNCTIONALIZATION OF SATURATED-HYDROCARBONS - GIF CHEMISTRY [J].
BARTON, DHR ;
DOLLER, D .
ACCOUNTS OF CHEMICAL RESEARCH, 1992, 25 (11) :504-512
[2]   A NEW AND EFFICIENT BIOMIMETIC SYSTEM FOR HYDROCARBON OXIDATION BY DIOXYGEN USING MANGANESE PORPHYRINS, IMIDAZOLE, AND ZINC [J].
BATTIONI, P ;
BARTOLI, JF ;
LEDUC, P ;
FONTECAVE, M ;
MANSUY, D .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (10) :791-792
[3]  
HO TL, 1973, SYNTHESIS-STUTTGART, P347
[4]   HIGHLY REACTIVE ORGANOLANTHANIDES - A MECHANISTIC STUDY OF CATALYTIC OLEFIN HYDROGENATION BY BIS(PENTAMETHYLCYCLOPENTADIENYL) AND RELATED 4F COMPLEXES [J].
JESKE, G ;
LAUKE, H ;
MAUERMANN, H ;
SCHUMANN, H ;
MARKS, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (26) :8111-8118
[5]  
KARASEVICH EI, 1993, KINET CATAL+, V34, P583
[6]   A CHEMICAL-MODEL OF CYTOCHROME-P-450 - MONO-OXYGENASE-LIKE ACTIVATION OF DIOXYGEN [J].
KARASEVICH, EI ;
KHENKIN, AM ;
SHILOV, AE .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (10) :731-732
[7]  
KARASEVICH EI, 1993, KINET CATAL+, V34, P577
[8]  
LU WY, 1992, NEW J CHEM, V16, P621
[9]   BASIC CHARACTER OF RARE-EARTH-METAL ALKOXIDES - UTILIZATION IN CATALYTIC C-C BOND-FORMING REACTIONS AND CATALYTIC ASYMMETRIC NITROALDOL REACTIONS [J].
SASAI, H ;
SUZUKI, T ;
ARAI, S ;
ARAI, T ;
SHIBASAKI, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (11) :4418-4420
[10]  
WATSON RL, 1985, ACCOUNTS CHEM RES, P51