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DOI: 10.1055/s-2008-1077876
A New Insight into the Oxidation of Cyclododecane with Hydrogen Peroxide in the Presence of Iron-Substituted Polyoxotungstates
Publikationsverlauf
Publikationsdatum:
11. Juni 2008 (online)
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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References and Notes
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 Aliquots were withdrawn from the reaction mixture and injected directly into GC-MS (fused silica capillary column, DB-5, with 30 m × 0.25 mm i.d.; 0.25 µm film thickness).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.
30The 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.