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Synlett 2003(11): 1643-1646
DOI: 10.1055/s-2003-41421
LETTER
© Georg Thieme Verlag Stuttgart · New York

Tungstoborates as Highly Active Catalysts for Cycloalkane Oxygenation Using Hydrogen Peroxide

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

Received 15 July 2003
Publication Date:
22 September 2003 (online)

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Abstract

Keggin-type tungstoborates [BW12O40]5-, Hx[BW11O39]9-x)- and [BM(H2O)W11O39]6-, M = FeIII, MnIII or RuIII proved to be highly active catalysts for the H2O2 oxidation of cyclooctane and cyclohexane to the corresponding ketone, alcohol and alkyl hydroperoxide derivatives. High turnover numbers and high selectivity for the hydroperoxide were observed.

Keywords

polyoxometalates - cycloalkanes - oxidation - hydrogen peroxide - tungstoborates

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23

The reactions were typically carried out by heating a solution of 1 mmol of the cycloalkane and 1.5 µmol of the catalyst in 1.5 mL of acetonitrile at 80 ºC. The oxidant used was 30% aqueous H2O2. Aliquots were withdrawn from the reaction mixture and injected directly into a GC-MS (fused silica Supelco capillary column, SPB-5, with 30 m × 0.25 mm i.d.; 0.25 µm film thickness).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.

25

For BFe an aqueous solution of BW11 was added to a solution of Fe(NO3)3·9H2O (order of addition reversed in comparison with BMn). TBA4H2BFe(H2O)W11O39·H2O Yield, 91%. Anal. Found: W, 55.0; Fe, 1.48; C, 20.53; H, 4.09, N, 1.56; hydration H2O, 0.51. Calcd: W, 54.4; Fe, 1.50; C, 20.60; H, 4.03, N, 1.50; hydration H2O, 0.48; IR (cm-1): 997 (m), 956(vs), 900(vs), 825(vs), 757 (s, sh), 528 (m). For preparation of BRu RuCl3·H2O was used. TBA4H2BRu(H2O)W11O39·2H2O Yield, 89%. Anal. Found: W, 54.2; Ru, 2.56; C, 20.58; H, 4.11, N, 1.72; hydration H2O, 1.02. Calcd: W, 53.5; Ru, 2.69; C, 20.30; H, 4.02, N, 1.48; hydration H2O, 0.95; IR (cm-1): 998 (m), 950 (vs), 902 (vs), 825 (vs), 743 (s, sh), 530 (m). µ = 1.99 µB.

27

The decomposition of H2O2 during the reaction was monitored by titration of aliquots with ceric sulphate. At the end of the reactions, the total of unused H2O2 and hydroperoxide produced was estimated by titration with ceric sulphate. From the yields of hydroperoxide (and cyclohexanol and cyclohexanone) determined by gas chromatography, the amount of H2O2 used in the reaction could be determined.