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Synlett 2008(11): 1623-1626  
DOI: 10.1055/s-2008-1077876
LETTER
© Georg Thieme Verlag Stuttgart · New York

A New Insight into the Oxidation of Cyclododecane with Hydrogen Peroxide in the Presence of Iron-Substituted Polyoxotungstates

Isabel C. M. S. Santosa, Mário M. Q. Simõesa, M. Salete S. Balulaa,b, M. Graça P. M. S. Nevesa, José A. S. Cavaleiroa, Ana M. V. Cavaleiro*a,b
a Chemistry Department, University of Aveiro, Universidade de Aveiro, 3810-193 Aveiro, Portugal
b CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
Fax: +351(234)370084; e-Mail: anacavaleiro@ua.pt;
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Publication History

Received 28 January 2008
Publication Date:
11 June 2008 (online)

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Abstract

The catalytic homogeneous oxidation of cyclododecane with hydrogen peroxide in the presence of tetrabutylammonium salts of iron-substituted Keggin-type polyoxotungstates of general formula (TBA)4HzXW11Fe(H2O)O39·nH2O (where X = P, Si, B, and z = 0-2) is described. In the reaction conditions reported, the corresponding alcohol, ketone, and hydroperoxide are obtained as the main reaction products. The catalytic activity of the anions with phosphorous, silicon, and boron is compared in different reaction conditions. These catalytic oxidation reactions seem to be radical processes, since they are totally inhibited in the presence of I2, a well-known radical scavenger.

Key words

iron - polyoxometalates - polyoxotungstates - oxidation - hydrogen peroxide - cyclododecane

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29

The reactions were typically carried out by heating a solution of 1.0 mmol of the cycloalkane and 1.5 µmol of the catalyst in MeCN at 80 °C. The oxidant used was 30 wt% aq H2O2. Aliquots were withdrawn from the reaction mixture and injected directly into GC-MS (fused silica capillary column, DB-5, with 30 m × 0.25 mm i.d.; 0.25 µm film thickness). The percentages of each compound in the reaction mixture were estimated directly from the corresponding chromatographic peak areas.

30

The efficiency of usage of hydrogen peroxide is calculated according to the following formula: (amount of ketone × 2 + amount of alcohol + amount of alkyl hydroperoxide × 2 + amount of aldehyde)/(amount of H2O2 used). The unused H2O2 and the hydroperoxide produced were quantified by titration of aliquots with 0.1 M Ce(SO4)2 using ferroin as indicator. From the yields of the hydroperoxide, determined by GC-MS, the amount of H2O2 used can be determined.