Oxidation of Alcohols with Hydrogen Peroxide

6 Catalytic Oxidation of Alcohols with Hydrogen Peroxide 

Titanium silicalite (TS-1), an isomorphously substituted molecular sieve [215], is a truly heterogeneous catalyst for oxidations with 30% aq. H202, including the oxidation of alcohols [216]. 

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Gelbard has used peroxotungstates supported on polypyridine polymers in the epoxidation of cyclohexene with hydrogen peroxide.66 Polypyridine polymers were also used to support heteropolyperoxometallates for use in the oxidation of alcohols with hydrogen peroxide.67 The tetranuclear complex [cetylpyridinium chloride][P04 WO(02)2 4] supported on polypyridine was found to be an effective catalyst for the oxidation of cyclohexanol to cyclohexanone, also with hydrogen peroxide. 

An interesting example of the use of a recyclable, thermoresponsive catalyst in a micellar-type system was recently reported by Ikegami et al. [38]. A PNI-PAM-based copolymer containing pendant tetraalkylammonium cations and a polyoxometalate, PW1204o, as the counter anion was used as a catalyst for the oxidation of alcohols with hydrogen peroxide in water (Fig. 9.25). At room temperature the substrate and the aqueous hydrogen peroxide, containing the catalyst, formed distinct separate phases. When the mixture was heated to 90 °C a... 

Fig. 9.25 Oxidation of alcohols with hydrogen peroxide using a thermoresponsive catalyst in a micellar system.

Chhikara BS, Chandra R, Tandon V (2005) Oxidation of alcohols with hydrogen peroxide catalyzed by a new imidazolium ion based phosphotungastate complex in ionic Uquid. J Catal... 

Scheme 9.15 Aqueous biphasic reactions via self-assembly for oxidation of alcohols with hydrogen peroxide.

The activity of some heterogeneous catalytic systems based on iron- and titanium-supported catalysts and hydrogen peroxide as oxidant was recently improved by utilization of MW irradiation. Thus, the MW-assisted oxidation of alcohols with hydrogen peroxide in water-acetonitrile media in the presence of various iron-, aluminum-, mixed iron/aluminum-, titanium-, and cobalt-supported (on MCM-41[26] and SBA-15 [27]) catalysts was reported recently [10b, 28], The supported iron nanoparticles (Fe-NPs) were prepared from a suspension of iron(II) chloride in ethanol under MW [28a], The preparation of Fe/Al-MCM-41 was similar, but with the use of the Al-derived support. The Ti- B-MCM-41 catalyst was prepared from... 

CATALYTIC OXIDATION OF ALCOHOLS WITH HYDROGEN PEROXIDE AND ALKYL HYDROPEROXIDES... 

Zhao, W., Zhang, Y., Ma, B., et al. (2010). Oxidation of Alcohols with Hydrogen Peroxide in Water Catalyzed by Recyclable Keggin-Type Tnngstoborate Catalyst, Catal. Common., 11, pp. 527-531. 

Wang, J., Yan, L., Li, G., et al. (2005). Mono-Substituted Keggin-Polyoxometalate Complexes as Effective and Recyclable Catalyst for the Oxidation of Alcohols with Hydrogen Peroxide in Biphasic System, Tetrahedron Lett., 46, pp. 7023-7027. 

Oxidation and Bromination of Alcohols. Although the oxidation of alcohols by hydrogen peroxide alone is negligible, catalytic amounts of bromide ions greatly enhance the rate of MTO-catalyzed oxidation of alcohols with hydrogen peroxide. Interestingly, a secondary alcohol has been selectively oxidized in the presence of a primary alcohol (eq 24). ... 

Farsani MR, YadoUahi B. Synthesis, characterization and catalytic performance of a Fe polyoxometalate/silica composite in the oxidation of alcohols with hydrogen peroxide. J Mol Catal A Chem. 2014 392 8-15. 

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