1-甲基-3,5-二苯基吡唑啉在氯化铜催化下的氧化脱氢反应(Ⅱ)——计量反应与氧分子的作用阶段

The Oxidative Dehydrogenation of 1-Methyl-3,5-Diphenyl- pyrazoline Catalyzed by Cupric Chloride (Ⅱ)——Stoichiometric Reaction and the Stage of Reaction with Oxygen’s Participation

我们在合成1-甲基-3,5-二苯基吡唑(MDPP)的过程中,发现氯化铜、氯化钴等化合物对1-甲基-3,5-二苯基吡唑啉(H_(2)MDPP)的氧化脱氢反应具有优异的催化性能^([1]),对以氯化铜为催化剂的反应机理进行了初步研究,获得了反应过程中形成铜(Ⅱ)H_(2)MDPP、铜(Ⅱ)MDPP和铜(Ⅱ)H_(2)MDPP分子氧配合物的证据^([2])。另外,在催化氧化反应体系中曾检测到一价铜,这显然是氯化铜的还原产物,故本文对氯化铜与H_(2)MDPP的计量反应及在催化反应中氧分子参与作用的阶段进行了研究。

Stoichiometric reaction of cupric chloride with 1 -methyl-3,5-diphcnylpyrazo-line(H_(2)MDPP) has been studied. It has been found that the chief product of the reaction closely resembles to a catalytic oxidation. From the Stoichiometric reaction mixture a coppcr( Ⅰ ) complex of H_(2)MDPP and 1-mcthy1-3,5-diphenylpyrazole (MDPP) has been isolated. The composition and IR spectrum of the complex have been obtained.It has been proved that the stage of reaction with the oxygen’ s participation took place before the reduction of coppcr( Ⅱ ) to copper( Ⅰ ) by the measurement of oxygen consumption in the reaction.