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首页> 外文期刊>Catalysis science & technology >Oxidative coupling of anilines to azobenzenes using heterogeneous manganese oxide catalysts
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Oxidative coupling of anilines to azobenzenes using heterogeneous manganese oxide catalysts

机译：偶氮苯氧化耦合的苯胺类使用异构锰氧化物催化剂

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摘要

We herein report the transition metal oxide-catalyzed synthesis of azobenzenes through the oxidative coupling of anilines. An octahedral molecular sieve of manganese oxide, OMS-2, exhibited the best activity and selectivity. Nine examples of symmetric azobenzenes and twenty unsymmetric ones were synthesized with 62-99% conversion and 64-99% selectivity. In the aniline cross-coupling reactions, the difference of the Hammett constants of two substituted groups (Delta sigma) determines the selectivity to unsymmetric azobenzenes, which are the major products at Delta sigma < 0.32. In-depth studies reveal that the surface defect sites of the mixed-valence manganese oxide play a key role in facilitating electron transfer and activating molecular oxygen. The single-electron transfer (SET) reaction mechanism is proposed based on electron paramagnetic resonance and X-ray powder diffraction characterization.
机译：我们在此报告的过渡金属oxide-catalyzed偶氮苯的合成苯胺类的氧化耦合。分子筛的锰氧化物、OMS-2表现出最好的活性和选择性。对称的偶氮苯和二十的例子不对称合成的62 - 99%转换和选择性64 - 99%。交叉耦合反应的差异哈米特常数两个替换组(δσ)决定了选择性不对称偶氮苯,是主要的产品δσ< 0.32。泄露的表面缺陷的网站混合价锰氧化物中发挥关键作用促进电子转移和激活分子氧。(套)反应机理提出了电子顺磁共振和x射线粉末衍射特性。

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