Guo Shiwei, Li Yinghua, Fan Weibin, Liu Zhiqi, Huang Deguang
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, China.
College of Materials Science and Opto Electronic Technology, University of Chinese Academy of Sciences, Beijing, China.
Front Chem. 2022 May 24;10:891858. doi: 10.3389/fchem.2022.891858. eCollection 2022.
A simple and efficient method for the synthesis of dialdehyde aniline in good yields (up to 83%) is explored using Cu(OTf) as the catalyst, Selectfluor as the radical initiator, and DMSO as both the carbon and oxygen sources. Experimental studies indicate that the reaction is achieved by the formylation of two C-H bonds, first at the para-position and then at the ortho-position. A possible mechanism is proposed, including the thermal homolysis of Selectfluor, the Cu(II)-facilitated formylation of the C-H bonds, and the hydrolysis of the amide under alkaline conditions in air atmosphere.
探索了一种以三氟甲磺酸铜为催化剂、Selectfluor为自由基引发剂、二甲基亚砜同时作为碳源和氧源，高产率（高达83%）合成二醛基苯胺的简单高效方法。实验研究表明，该反应通过两个C-H键的甲酰化反应实现，首先是对位的甲酰化，然后是邻位的甲酰化。提出了一种可能的机理，包括Selectfluor的热均裂、Cu(II)促进的C-H键甲酰化以及在空气气氛碱性条件下酰胺的水解。
