Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S_NAr and Cross-Coupling Reactions

Abstract

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

• sulfur–nitrogen heterocycles
• benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole)
• aromatic nucleophilic substitution
• Suzuki and Stille cross-coupling reactions
• X-ray analysis