Synthesis of Core-Functionalised Naphthalenediimides from Naphthalenetetracarboxylic Dianhydride using a Vibratory Ball Mill: Bromination, Imidization and Heck-Type Reactions.

The synthesis of 9 core-functionalised naphthalene diimide (c-NDI) residues is reported via a 3-step synthesis from naphthalenetetracarboxylic dianhydride using only mechanochemical activation. Selective dibromination and subsequent diimidization were achieved for the first time in a vibratory ball mill, resulting in the key structural intermediate, 2,6-dibromonaphthalenediimide (DBND), which is the basis for elaboration into a multitude of organic electronic materials. Our new synthesis of DBND is achieved in just 5 hours reaction time over two steps compared to typical solution state times of 24 hours. Subsequent Heck-type cross coupling reactions, with a range of styrene residues, produced a series of c-NDIs in good yields. The Heck-type reactions are rapid (1.5 hours), require no additional heating or solvent and are tolerant of atmospheric moisture and air.