Experimental evidence for a dual site mechanism in Sn-Beta and Sn-MCM-41 catalysts for the Baeyer-Villiger oxidation

被引：12

作者：

Corma, A ^{[1
]}

Renz, M ^{[1
]}

机构：

[1] Univ Politecn Valencia, CSIC, Inst Technol, Valencia 46022, Spain

来源：

COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS | 2005年 / 70卷 / 10期

关键词：

heterogeneous catalysis; Knoevenagel-type condensation; malononitrile; ketones; Sn-Beta; Sn-MCM-41; zeolites; MAS NMR spectroscopy;

D O I：

10.1135/cccc20051727

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

It is postulated that the catalytic active centre in Sn-Beta and Sn-MCM-41 zeolites for Baeyer-Villiger oxidations involves not only the framework Sn sites but also an associated "basic" oxygen that stabilises the reaction transition state through hydrogen bonding. The presence of these "basic" sites has been studied by cross-polarization MAS NMR H -> Sn, and by carrying out the condensation of ketones with malononitrile. The reaction proceeds highly selectively and the reactivity of the substrates corresponds to that of the ketones in the Baeyer-Villiger oxidation with hydrogen peroxide, catalysed with tin-containing molecular sieves.

引用

页码：1727 / 1736

页数：10

共 18 条

[1] KNOEVENAGEL CONDENSATION IN THE HETEROGENEOUS PHASE USING ALPO4-AL2O3 AS A NEW CATALYST [J].

CABELLO, JA ;

CAMPELO, JM ;

GARCIA, A ;

LUNA, D ;

MARINAS, JM .

JOURNAL OF ORGANIC CHEMISTRY, 1984, 49 (26) :5195-5197

[2] Increasing the basicity and catalytic activity of hydrotalcites by different synthesis procedures [J].

Climent, MJ ;

Corma, A ;

Iborra, S ;

Epping, K ;

Velty, A .

JOURNAL OF CATALYSIS, 2004, 225 (02) :316-326

[3]

Climent MJ, 2002, ADV SYNTH CATAL, V344, P1090, DOI 10.1002/1615-4169(200212)344:10<1090::AID-ADSC1090>3.0.CO

[4]

2-X

[5] Sn-Beta zeolite as diastereoselective water-resistant heterogeneous Lewis-acid catalyst for carbon-carbon bond formation in the intramolecular carbonyl-ene reaction [J].

Corma, A ;

Renz, M .

CHEMICAL COMMUNICATIONS, 2004, (05) :550-551

[6] Water-resistant solid Lewis acid catalysts: Meerwein-Ponndorf-Verley and Oppenauer reactions catalyzed by tin-beta zeolite [J].

Corma, A ;

Domine, ME ;

Valencia, S .

JOURNAL OF CATALYSIS, 2003, 215 (02) :294-304

[7] AI-free Sn-beta zeolite as a catalyst for the selective reduction of carbonyl compounds (Meerwein-Ponndorf-Verley reaction) [J].

Corma, A ;

Domine, ME ;

Nemeth, L ;

Valencia, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (13) :3194-3195

[8] Sn-MCM-41 - a heterogeneous selective catalyst for the Baeyer-Villiger oxidation with hydrogen peroxide [J].

Corma, A ;

Navarro, MT ;

Nemeth, L ;

Renz, M .

CHEMICAL COMMUNICATIONS, 2001, (21) :2190-2191

[9] Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-Villiger oxidations [J].

Corma, A ;

Nemeth, LT ;

Renz, M ;

Valencia, S .

NATURE, 2001, 412 (6845) :423-425

[10] Kinetics of the oxidation of alcohols by hydrogen peroxide on Ti-beta zeolite: The influence of alcohol structure on catalyst reactivity [J].

Corma, A ;

Esteve, P ;

Martinez, A .

APPLIED CATALYSIS A-GENERAL, 1996, 143 (01) :87-100

← 1 2 →