Li Shiyun, Zhao Wei, Wang Lulu, Jia Yixiong, Cui Qingyan, Wen Bin, Chen Xingquan
College of Chemical Engineering, Fuzhou University, Fuzhou 350108, China.
Qingyuan Innovation Laboratory, Quanzhou 362801, China.
ACS Omega. 2024 Sep 11;9(38):39715-39723. doi: 10.1021/acsomega.4c04820. eCollection 2024 Sep 24.
The importance of selectively oxidizing aniline into value-added chemicals azoxybenzene and nitrobenzene is well-recognized in organic synthesis. However, the lack of control over selectivity and the complex synthesis of costly catalysts significantly hinder these reactions' industrial applications. In this work, an environmentally friendly approach was developed for the selective oxidization of substituted anilines. This method involves adjusting the strength of alkalinity with peroxide as the oxidant, without the addition of any metals or additives. A mild base (NaF) facilitated azoxybenzene formation, while a stronger base (NaOMe) enabled the synthesis of nitroaromatics. These protocols are user-friendly and scalable, accommodating various substitution patterns and functional groups, yielding products with high to excellent yields. The findings of this work present a framework for investigating base catalysis in organic synthesis and provide a viable and effective approach for selectively oxidizing aniline.
在有机合成中，将苯胺选择性氧化为高附加值化学品偶氮苯和硝基苯的重要性已得到广泛认可。然而，缺乏对选择性的控制以及昂贵催化剂的复杂合成严重阻碍了这些反应的工业应用。在这项工作中，开发了一种用于选择性氧化取代苯胺的环境友好方法。该方法涉及用过氧化物作为氧化剂调节碱度强度，无需添加任何金属或添加剂。温和的碱（NaF）促进偶氮苯的形成，而更强的碱（NaOMe）则能实现硝基芳烃的合成。这些方案操作简便且可扩展，适用于各种取代模式和官能团，产物收率高至优异。这项工作的发现为研究有机合成中的碱催化提供了一个框架，并为选择性氧化苯胺提供了一种可行且有效的方法。
