Barišić Dajana, Pajić Mario, Halasz Ivan, Babić Darko, Ćurić Manda
Division of Physical Chemistry, Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, Croatia.
Beilstein J Org Chem. 2022 Jun 15;18:680-687. doi: 10.3762/bjoc.18.69. eCollection 2022.
The direct and selective mechanochemical halogenation of C-H bonds in unsymmetrically substituted azobenzenes using -halosuccinimides as the halogen source under neat grinding or liquid-assisted grinding conditions in a ball mill has been described. Depending on the azobenzene substrate used, halogenation of the C-H bonds occurs in the absence or only in the presence of Pd catalysts. Insight into the reaction dynamics and characterization of the products was achieved by in situ Raman and ex situ NMR spectroscopy and PXRD analysis. A strong influence of the different 4,4'-substituents of azobenzene on the halogenation time and mechanism was found.
本文描述了在球磨机中，以卤代琥珀酰亚胺为卤素源，在纯研磨或液体辅助研磨条件下，对不对称取代偶氮苯中的C-H键进行直接和选择性的机械化学卤化反应。根据所使用的偶氮苯底物，C-H键的卤化反应在无钯催化剂或仅在钯催化剂存在的情况下发生。通过原位拉曼光谱、非原位核磁共振光谱和粉末X射线衍射分析，深入了解了反应动力学和产物特性。研究发现，偶氮苯不同的4,4'-取代基对卤化时间和反应机理有很大影响。
