Selective epoxidation of cyclohexene to cyclohexene oxide catalyzed by Keggin-type heteropoly compounds using anhydrous urea-hydrogen peroxide as oxidizing reagent and acetonitrile as the solvent

被引：75

作者：

Ding, Y

Gao, Q

Li, GX

Zhang, HP

Wang, JM

Yan, L

Suo, JS ^{[1
]}

机构：

[1] Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China

[2] Chinese Acad Sci, Chengdu Organ Chem Co Ltd, Beijing 100864, Peoples R China

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2004年 / 218卷 / 02期

关键词：

epoxidation; cyclohexene; urea-hydrogen peroxide; Keggin-type heteropoly compounds; acetonitrile;

D O I：

10.1016/j.molcata.2004.04.019

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 epoxidation of cyclohexene catalyzed by Keggin-type heteropoly compounds (HPAs) were investigated using anhydrous urea-hydrogen peroxide adduct (UHP) as an oxidant and acetonitrile as a solvent. Among a series of Keggin-type heteropoly compounds, tris(cetylpyridinium) 12-tungstopbosphate (CWP) showed the highest activity. By optimizing the reaction conditions, 80% conversion of cyclohexene and 97% selectivity for cyclobexene oxide could be achieved in the UHP/CH3CN system. When aqueous 30% hydrogen peroxide (H2O2, HP) was used, the cyclohexene conversion and cyclohexene epoxide selectivity were inferior to those obtained with the UHP/CH3CN system. The reaction of UHP with CWP has been studied by UV-Vis and P-31 NMR spectroscopy, which has revealed that the Keggin-type heteropoly compounds CWP is degraded in the presence of excess UHP to form a considerable amount of phosphorus-containing species. (C) 2004 Elsevier B.V. All rights reserved.

引用

页码：161 / 170

页数：10

共 46 条

[1]

[Anonymous], REV HETEROATOM CHEM

[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] REACTIVITY OF PEROXOPOLYOXO COMPLEXES - OXIDATION OF THIOETHERS, ALKENES, AND SULFOXIDES BY TETRAHEXYLAMMONIUM TETRAKIS(DIPEROXOMOLYBDO)PHOSPHATE [J].

BALLISTRERI, FP ;

BAZZO, A ;

TOMASELLI, GA ;

TOSCANO, RM .

JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (26) :7074-7077

[4]

BOESCHEN F, 1994, ACTA CRYSTALLOGR B, V30, P48

[5] THE INFRA-RED SPECTRA OF SOME 12-HETEROPOLYTUNGSTATES [J].

BROWN, DH .

SPECTROCHIMICA ACTA, 1963, 19 (02) :585-587

[6] STUDIES ON TRANSITION-METAL PEROXO COMPLEXES .8. THE NATURE OF PEROXOMOLYBDATES AND PEROXOTUNGSTATES IN AQUEOUS-SOLUTION [J].

CAMPBELL, NJ ;

DENGEL, AC ;

EDWARDS, CJ ;

GRIFFITH, WP .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (06) :1203-1208

[7] SYNTHESIS OF PROPYLENE-OXIDE FROM PROPYLENE AND HYDROGEN-PEROXIDE CATALYZED BY TITANIUM SILICALITE [J].

CLERICI, MG ;

BELLUSSI, G ;

ROMANO, U .

JOURNAL OF CATALYSIS, 1991, 129 (01) :159-167

[8] PEROXO-OXOMETALLATE FORMATION UNDER PHASE-TRANSFER CONDITIONS [J].

CSANYI, LJ ;

JAKY, K .

JOURNAL OF MOLECULAR CATALYSIS, 1990, 61 (01) :75-84

[9] SOME FEATURES OF EPOXIDATION OF CYCLOHEXENE CATALYZED BY OXOPEROXOMETALLATES UNDER PHASE-TRANSFER CONDITIONS [J].

CSANYI, LJ ;

JAKY, K .

JOURNAL OF CATALYSIS, 1991, 127 (01) :42-50

[10] MECHANISM AND DYNAMICS IN THE H-3[PW12O40]-CATALYZED SELECTIVE EPOXIDATION OF TERMINAL OLEFINS BY H2O2 - FORMATION, REACTIVITY, AND STABILITY OF (PO4[WO(O-2)(2)](4))(3-) [J].

DUNCAN, DC ;

CHAMBERS, RC ;

HECHT, E ;

HILL, CL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (02) :681-691

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