Catalytic activity of tetravalent metal phosphates and phosphonates on the oxidation of (+)-3-carene

Tetravalent metal phosphates and phosphonates form highly insoluble inorganic polymers and can act as good catalysts in some oxidative reactions. In the present work, zirconium phosphate amorphous (ZrPA), scandium exchanged zirconium phosphate amorphous (ScZrPA), sodium exchanged zirconium phosphate amorphous (NaZrPA), potassium exchanged zirconium phosphate amorphous (KZrPA), zirconium phenylphosphonate amorphous (ZrPPA) and zirconium phenylphosphonate phosphate amorphous (ZrPA/ZrPPA), were prepared and evaluated as catalysts for the oxidation of 3,7,7-trimethylbicyclo[4.1.0]hept-3-ene [(+)-3-carene)] by hydrogen peroxide, in different solvents. It was found that the oxidation reaction of (+)-3-carene yielded three major products, namely alpha-3,4-epoxycarane, carane-3 beta,4 alpha-diol and 3 beta-acetoxycaran-4 alpha-ol, depending on the catalyst and solvent conditions. No beta-3,4-epoxycarane was detected in the studied conditions. (C) 2008 Elsevier B.V. All rights reserved

Oxidation of bicyclic arenes with hydrogen peroxide catalysed by Mn(III) porphyrins

Several manganese(III) porphyrin complexes were evaluated as catalysts in the oxidation of indane and tetralin with hydrogen peroxide, in the presence of ammonium acetate as a co-catalyst. Catalysis by Mn(Ill) meso-tetra-2,6-dichlorophenylporphyrins gave rise, in a first stage, to benzylic monooxygenation products (1-alcohols and 1-ketones). However, addition of excess of oxidant gave rise to overoxidation products and, in certain conditions, hydroxy-keto compounds were selectively obtained. Reactions catalysed by Mn(Ill) mesotetra-pentafluorophenylporphyrins showed higher capability to generate dehydrogenated products. As a result, 1H-indene and naphthalene were formed. To understand the reactions' pathway, the oxidations of 1-indanol, 1-indanone, 2-indanol, 1H-indene, 1-tetralol, 1-tetralone, 1,4-dihydroxytetralin and 4-hydroxy-1-tetralone were also considered with manganese (111) meso-tetra-2,6-dichlorophenylporphyiin chloride, Mn(TDCPP)Cl, as catalyst. (c) 2005 Elsevier B.V. All rights reserved

Iron(III)-substituted polyoxotungstates immobilized on silica nanoparticles: novel oxidative heterogeneous catalysts

Supplementary materials related to this article can be found online at doi:10.1016/j.catcom.2010.11.005.Silica nanoparticles supporting polyoxometalates (POMs), namely an iron(III) mono-substituted Keggin-type polyoxotungstate of formula alpha-[PW(11)Fe(III)(H(2)O)O(39)](4-) and a sandwich-type tungstophosphate with the formula B-alpha-[(PW(9)O(34))(2)Fe(4)(III)(H(2)O)(2)](6-) were synthesized. The POM/SiO(2) nanocomposites were obtained by alkaline hydrolysis of tetraethoxysilane using a reverse micelle and sol-gel technique. The spectroscopic studies suggest that the POMs were successfully immobilized on the silica nanoparticles. The catalytic activity of POM/SiO(2) nanomaterials was tested in the epoxidation of geraniol using H(2)O(2) as oxygen donor. The alpha-[PW(11)Fe(III)(H(2)O)O(39)](4-)/SiO(2) nanocomposite was the most efficient catalyst with high geraniol conversion and good regioselectivity for 2,3-epoxygeraniol. (C) 2010 Elsevier B.V. All rights reserved.FCT/FEDER for funding CICECO and QOPN