Oxidation with the “O2?H2O2?VO3 ??pyrazine-2-carboxylic acid” reagent

n-Heptane is readily oxidized in acetonitrile under the action of H₂O₂ with a “vanadate anion-pyrazine-2-carboxylic acid” system as the catalyst in air to form isomeric heptyl hydroperoxides (detected by GLC) along with isomeric heptanols and heptanones. Heptyl hydroperoxides slowly decompose at low temperature yielding the corresponding alcohols and ketones (aldehyde). The values of the parameter of the relative normalized reactivity of the H atoms at the carbon atoms in positions 1, 2, 3 and 4 depend on the reaction time and concentrations of the reagents. The value of the parameter of selectivity C(1)∶C(2)∶C(3)∶ C(4) varies in the range from 1.0∶2.8∶2.9∶1.8 to 1.0∶5.6∶5.9∶5.3 The low selectivity of the reaction shows that the key role is played by the attack of highly reactive radical particles on the C−H bond of the alkane molecule. For Part 5, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 780–785, April, 1997.