In conclusion, we have developed methods for the preparation of a wide range of 5,6-dihalobenzene-1,2,3,4-bis(dicarboximides) from the direct solution-phase condensation of benzene-1,2,3,4-tetracarboxylic acids and primary amines in acetic acid solvent. The preparation of compounds with sterically demanding groups at the N atoms of the imides can be achieved readily under microwave conditions. Experimental and computational studies suggest that the reaction can take place under equilibrium conditions that are favored both statistically and thermodynamically to yield the desired ortho-diimide compounds instead of the symmetric dicarboxyphthalimide. Importantly, it is possible to avoid perturbing the aryl halide positions under these reaction conditions, which sets the stage for exploring a broad range of chemistries available for producing imide-decorated aromatic compounds with tailored form and function.