Synthesis of stable class 5 mesoionic benzo[c]tetrazolo[2,3-a]cinnolinium thiolate, dicyanomethylide, and amides

Although class 5 mesoionic compounds show interesting electrical behaviour, they are generally unstable, readily undergoing ring-opening reactions. We designed and synthesized a bridged mesoionic derivative, benzo[c]tetrazolo[2,3-a]cinolinium (BTC), as a stable class 5 mesoionic compound, which was further transformed to the corresponding thiolate, cicyanomethylide, and amide. The intramolecular bridging imparted stability to the BTC thiolates and amides: the BTC thiolates were unsusceptible to ring-opening at high temperatures, and the BTC amides were stable in the absence of electron-withdrawing groups on the amide nitrogen. The properties of the BTC thiolate were compared with those of 2,3-diphenyltetrazolium derivatives based on UV-Vis absorption spectroscopy, single-crystal X-ray diffraction and quantum calculations.