过氧化氢水溶液催化氧化环戊烯制备戊二醛机理研究

Studies on the Mechanism of Catalytic Oxidation of Cyclopentene to Prepare Glutaraldehyde with Aqueous Hydrogen Peroxide

在钨酸-叔丁醇体系中,用H_2O_2水溶液氧化环戊烯制备戊二醛的机理是:环戊烯首先氧化成环戊烯氧化物,然后生成过氧化物中间物,经分离检定,确证为β-羟基环戊基过氧化氢,中间物再进行重排,形成戊二醛产物.在H_2O_2等量的情况下,重排只能部分进行,加大H_2O_2用量,可以使中间物在常温下重排接近完全.

The mechanism of catalytic oxidation of cyclopentene with aqueous hydrogen peroxide to prepare glutaraldehyde in a tungstic acid-tert-butanol system is that, first, cyclopentene was oxidized to cyclopentene oxide almost quantitively; then the latter was turned into an intermediate-a kind of organic peroxide, which was separated and identified as β-hydroxy-cyclopentylperoxide. At room temperature, it can be rearranged into glutaraldehyde near completely catalyzed by W(VI) in a system containing excessive hydrogen peroxide.