An efficient synthesis of hydrolytically and thermally stable 4,8-dibromobenzo[1,2-d:4,5-d']bis([1,2,3]thiadiazole) by the bromination of its parent heterocycle is reported. The structure of 4,8-dibromobenzo[1,2-d:4,5-d']bis([1,2,3]thiadiazole) was confirmed by X-ray analysis. The conditions for the selective aromatic nucleophilic substitution of one bromine atom in this heterocyclic system by nitrogen nucleophiles are found, whereas thiols formed the bis-derivatives only. Suzuki-Miyaura cross-coupling reactions were found to be an effective method for the selective formation of various mono- and di(het)arylated derivatives of strong electron-deficient benzo[1,2-d:4,5-d']bis([1,2,3]thiadiazole), and Stille coupling can be employed for the preparation of bis-arylated heterocycles, which can be considered as useful building blocks for the synthesis of DSSCs and OLEDs components.
Keywords: Suzuki and Stille cross-coupling reactions; X-ray analysis; aromatic nucleophilic substitution; benzo[1,2-d:4,5-d’]bis([1,2,3]thiadiazole); sulfur–nitrogen heterocycles.