Oxidation with the ''O-2-H2O2-VO3--pyrazine-2-carboxylic acid'' reagent .6. Oxidation of n-heptane and cyclochexane. Direct determination of alkyl hydroperoxides by gas-liquid chromatography

被引:31
作者
Guerreiro, MC
Schuchardt, U
Shulpin, GB
机构
[1] RUSSIAN ACAD SCI,NN SEMENOV CHEM PHYS INST,MOSCOW 117977,RUSSIA
[2] UNIV ESTADUAL CAMPINAS,INST QUIM,BR-13083970 CAMPINAS,SP,BRAZIL
关键词
metallocomplex catalysis; oxidation; hydrogen peroxide; vanadium complexes; alkanes; n-heptane; cyclohexane; activation of C-H bonds;
D O I
10.1007/BF02495206
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
n-Heptane is readily oxidized in acetonitrile under the action of H2O2 with a ''vanadate anion-pyrazine-2-carboxyiic 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.
引用
收藏
页码:749 / 754
页数:6
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