OXIDATION OF ALKYLAROMATIC COMPOUNDS WITH HYDROGEN-PEROXIDE CATALYZED BY MIXED ADDENDA KEGGIN HETEROPOLYANIONS

被引:66
作者
NEUMANN, R
DELAVEGA, M
机构
[1] Casali Institute of Applied Chemistry, Graduate School of Applied Science and Technology, The Hebrew University of Jerusalem, Jerusalem
来源
JOURNAL OF MOLECULAR CATALYSIS | 1993年 / 84卷 / 01期
关键词
HETEROPOLYANION; HYDROGEN PEROXIDE; MOLYBDENUM; OXIDATION; POLYOXOMETALATES; VANADIUM;
D O I
10.1016/0304-5102(93)80088-C
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
Keggin type mixed addenda heteropolyanions containing vanadium atoms such as PV2Mo10O405- are shown to be effective catalysts for the oxidation of alkylaromatic compounds to the respective acetates or alcohols and aldehydes or ketones using 30% hydrogen peroxide as oxidant. Use of spectroscopic techniques including UV-Vis, IR, vanadium-51 and phosphorus-31 NMR, and ESR shows that the H5PV2Mo10O40 compound is not degraded during the catalytic cycle. Oxidation proceeds by homolytic cleavage of H5P2Mo10O40-peroxo intermediates. The resulting hydroperoxy and hydroxy radicals initiate the formation of benzyl radicals which lead to the product formation.
引用
收藏
页码:93 / 108
页数:16
相关论文
共 44 条
[1]   HYDROGEN-PEROXIDE OXIDATION OF ALKYL AROMATIC-HYDROCARBONS CATALYZED BY KEGGIN-TYPE POLYOXOMETALATES [J].
ATTANASIO, D ;
ORRU, D ;
SUBER, L .
JOURNAL OF MOLECULAR CATALYSIS, 1989, 57 (01) :L1-L4
[2]   REINVESTIGATION OF EPOXIDATION USING TUNGSTEN-BASED PRECURSORS AND HYDROGEN-PEROXIDE IN A BIPHASE MEDIUM [J].
AUBRY, C ;
CHOTTARD, G ;
PLATZER, N ;
BREGEAULT, JM ;
THOUVENOT, R ;
CHAUVEAU, F ;
HUET, C ;
LEDON, H .
INORGANIC CHEMISTRY, 1991, 30 (23) :4409-4415
[3]  
BALISTRERI FP, 1989, J ORG CHEM, V54, P947
[4]  
BREGEAULT JM, 1989, CR ACAD SCI II, V309, P459
[5]  
BREGEAULT JM, 1991, DIOXYGEN ACTIVATION, P521
[6]  
CHAMBERS RC, 1989, INORG CHEM, V28, P2511
[7]   METAL-OXIDE CHEMISTRY IN SOLUTION - THE EARLY TRANSITION-METAL POLYOXOANIONS [J].
DAY, VW ;
KLEMPERER, WG .
SCIENCE, 1985, 228 (4699) :533-541
[8]   THE OXIDATION OF KETONES WITH A HETEROPOLYACID, H5[PMO10V2O40] AND DIOXYGEN [J].
ELALI, B ;
BREGEAULT, JM ;
MERCIER, J ;
MARTIN, J ;
MARTIN, C ;
CONVERT, O .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (13) :825-826
[9]   PHOTOACTIVATION OF METAL-OXIDE SURFACES - PHOTOCATALYZED OXIDATION OF ALCOHOLS BY HETEROPOLYTUNGSTATES [J].
FOX, MA ;
CARDONA, R ;
GAILLARD, E .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (21) :6347-6354
[10]   OXIDATION OF CYCLOPENTENE WITH HYDROGEN-PEROXIDE CATALYZED BY 12-HETEROPOLY ACIDS [J].
FURUKAWA, H ;
NAKAMURA, T ;
INAGAKI, H ;
NISHIKAWA, E ;
IMAI, C ;
MISONO, M .
CHEMISTRY LETTERS, 1988, (05) :877-880