A higher 1-olefin (1-dodecene) was oxidized to 2-dodecanone and other ketones in a modified Wacker system featured by omitting the use of copper chloride and employing tert-butylhydroperoxide (TBHP) as oxidant. Acetonitrile was the solvent of choice due to its higher selectivity towards 2-dodecanone, the reaction occurring mostly in the interface. A maximum in conversion and selectivity was measured for a ratio [CH3CN]/ [1-dodecene] = 10. The temperature abatement enhances the 2-dodecanone selectivity (61% at 40 degrees C) because of the lower extent of the competing isomerization reactions. An optimum in 2-dodecanone selectivity was found for a [TBHP/[1-dodecene] ratio = 7. The use of H2O2 as oxidant led towards slower oxidation rates than TBHP. Other palladium salts (PdSO4 and Pd(CH3COO)(2)) and several R-CN solvents (propionitrile, benzonitrile, isobutyronitrile) yielded lower performances than palladium chloride and acetonitrile, respectively. On the contrary, beta-cyclodextrin, a phase transfer catalyst, improved the selectivity towards 2-dodecanone. (c) 2007 Elsevier B.V. All rights reserved.