Synthesis of stable class 5 mesoionic benzo[]tetrazolo[2,3-]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[]tetrazolo[2,3-]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.

Synthesis of 3-(phenylazo)-1,2,4-triazoles by a nucleophilic reaction of primary amines with 5-chloro-2,3-diphenyltetrazolium salt via mesoionic 2,3-diphenyltetrazolium-5-aminides.

The reactions of a 5-chloro-2,3-diphenyltetrazolium salt with amines have been examined. In the presence of an inorganic base such as NaHCO(3), primary and secondary amines undergo a nucleophilic substitution to give the corresponding 5-aminotetrazolium salts. When triethylamine is used as a base, primary amines give 3-phenylazo-1,2,4-triazoles.