Journal
TETRAHEDRON
Volume 65, Issue 12, Pages 2424-2429Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.tet.2009.01.088
Keywords
Alkanes; Alkyl hydroperoxides; Cyclohexane; Homogeneous catalysis; Hydrogen peroxide; Oxidation; Vanadium complexes
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Funding
- Fundacao para a Ciencia e a Tecnologia (FCT)
- POCI 2010 programme (FEDER) [BPD/34926/07]
- AQUACHEM [MRTN-CT-2003-503864]
- Russian Foundation for Basic Research [06-03-32344-a]
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A simple system is described, which oxidizes saturated hydrocarbons either in acetonitrile or (less efficiently) in water. The system consists of 50% aqueous hydrogen peroxide as an oxidant, sodium metavanadate, NaVO3, as a catalyst and sulfuric (or oxalic) acid as a co-catalyst. The reactions were carried out at 20-50 degrees C. In the oxidation of cyclohexane in acetonitrile, the highest yield (37% based on cyclohexane) and turnover number (TON=1700) were attained after 3 h at 50 degrees C. The corresponding parameters were 16% and 1090 for n-heptane oxidation under the same conditions. The oxidation of higher alkanes. RH, in acetonitrile gives almost exclusively the corresponding alkyl hydroperoxides, ROOH. Light alkanes (n-butane, propane, ethane, and methane) have been also oxygenated by the system under consideration. The highest TON (200) was attained for ethane and the highest yield (19%) was obtained in the case of n-butane. The selectivity parameters measured for the oxidation of linear and branched alkanes are low, the reaction with cis- and trans- 1,2-dimethylcyclohexanes is not stereo-selective. These facts lead us to conclude that the oxidation occurs with the formation of hydroxyl radicals in the crucial step. (C) 2009 Elsevier Ltd. All rights reserved
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