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 N-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 PdII 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.