AbstractTreatment of 2,3,5,6‐tetraphenylpyrazine (1) with sodium in tetrahydrofuran effected the formation of monomeric dianion2. The chemical behaviour of this new disodium adduct was characterized by a variety of reagents. Generally, the protonation (water), alkylation (methyl iodide and benzyl chloride), and acylation (methyl and ethyl chloroformate) products were 1,2‐dihydrotetraphenyldiazine derivatives. An annulation of the pyrazine ring system was accomplished by treating the dianion with polymethylene chlorides, Cl(CH2)nCl,n= 2, 3