Self-assembled Na12[WZn3(ZnW9O 34)2] as an industrially attractive multi-purpose catalyst for oxidations with aqueous hydrogen peroxide

Organic Process Research and Development

Volumn 8, Issue 3, 2004, Pages 524-531

  Witte, Peter T ^a   Alsters, Paul L ^a   Jary, Walther ^b   Müllner, Ruth ^b   Pöchlauer, Peter ^b   Sloboda Rozner, Dorit ^c   Neumann, Ronny ^c  

^a DSM Pharmaceutical Products   (Netherlands)

^b DSM Fine Chemicals Austria Nfg GmbH & Co KG   (Netherlands)

^c WEIZMANN INSTITUTE OF SCIENCE   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN PEROXIDE; TUNGSTEN DERIVATIVE; ZINC DERIVATIVE;

AQUEOUS SOLUTION; ARTICLE; CATALYSIS; CATALYST; EPOXIDATION; OXIDATION; REACTION OPTIMIZATION; STOICHIOMETRY;

EID: 3042694819     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op034184o     Document Type: Article

References (43)

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16. 2 with concomitant formation of a peroxo W-species.
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23. Conversion/time profiles at varying stirring rates were independent of the rate of stirring above 200 rpm.
24. Ishii also attributes the higher activity of the in situ Ishii system compared to the isolated catalyst to the higher acidity as a result of HCl evolution, see ref 10. A rate-enhancing effect of acidity in Venturello-type epoxidations has also been reported: Wang, M. L.; Huang, T. H.; Wu, W. T. Ind. Eng. Chem. Res. 2002, 41, 518-523.
25. 2 systems. Note from ref 24 that HCl does have a positive effect on the Ishii system.
26. The pH of an aqueous solution of NaZnPOM prepared according to eq 1 is 7.5.
27. Even although many reactivity differences between the various catalyst systems can be understood qualitatively from differences in acidity, a simple reasoning based on acidity alone cannot account for all the differences, as has been pointed out in ref 25.
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29. For these experiments, isolated, crystalline NaZnPOM was used (prepared according to ref 7).
30. +, thus necessitating the use of more QCl.
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32. -1; TON = 2100.
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35. In addition, phosphate might influence catalyst performance through interaction with the polyoxotungstate, analogous to the Venturello system.
36. See: http://www.basf.com/businesses/consumer/cosmeticingredients/html/ mquaternary.html.
37. Obviously, use of isolated peroxo-type catalysts (Venturello, Prandi) is not feasible on a large scale.
38. A W-catalyst stock solution (92 μL; 0.27 mol W/L) of isolated QZnPOM or QMnPOM (0.014 mol/L) in toluene was added. See ref 4 for the preparation of stock solutions.
39. A W-catalyst stock solution (92 μL; 0.27 mol W/L) of isolated Venturello (0.068 mol/L) in toluene was added. See ref 11 for the preparation of stock solutions.
40. A W-catalyst stock solution (92 μL; 0.27 mol W/L) of isolated Prandi (0.135 mol/L) in toluene was added. Ishii isolated was added as a solid (7.9 mg, 2.1 μmol).
41. In reactions without solvent, the phase transfer catalyst was added as a solution in the required amount of cyclooctene.
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