期刊
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
卷 218, 期 2, 页码 171-177出版社
ELSEVIER
DOI: 10.1016/j.molcata.2004.04.025
关键词
alkanes; alkyl hydroperoxides; cyclohexane; ethane; homogeneous catalysis; methane; peroxy acids; peroxyacetic acid; oxidation; vanadium complexes
Peroxyacetic acid (PAA) oxidizes alkanes in acetonitrile or acetic acid at 60degreesC if a soluble vanadium(V) salt, n-Bu4NVO3 (1), is used as a catalyst. Corresponding ketones, alcohols and alkyl hydroperoxides are the main products. Methane, ethane, propane, cyclohexane, and other higher alkanes were substrates in the oxidations. The proposed mechanism involves the formation of a complex between (1) and PAA with equilibrium constants 3.3 and 6.8 dm(3) mol(-1) for acetonitrile and acetic acid as solvents, respectively. This complex decomposes to produce CH3C(=O)OO. radical and a V-IV derivative. The latter reacts with PAA to generate a CH3C(=O)O-. radical which attacks the alkane abstracting its hydrogen atom. An alkyl radical thus formed adds rapidly a molecule of dioxygen which leads finally to the alkyl hydroperoxide and then to the ketone and alcohol. Other vanadium(V) and vanadium(IV) complexes are also active in this oxidation only if the vanadium ion is not shielded with strongly bound bulky ligands. (C) 2004 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据