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Mechanochemical halogenation of unsymmetrically substituted azobenzenes

Dajana Barišić, Mario Pajić, Iván Halász, Darko Babić, Manda Ćurić

2022Beilstein Journal of Organic Chemistry14 citationsDOIOpen Access PDF

Abstract

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 Pd II 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.

Topics & Concepts

HalogenationAzobenzeneChemistryMechanochemistryRaman spectroscopyHalogenCatalysisGrindingBall millPhotochemistryIntramolecular forceOrganic chemistryMedicinal chemistryMoleculeChemical engineeringMaterials scienceEngineeringOpticsComposite materialPhysicsAlkylCatalytic C–H Functionalization MethodsPhenothiazines and Benzothiazines Synthesis and ActivitiesCrystallography and molecular interactions
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