New heterocyclic tetracyclic systems were synthesized. Interaction between 3-R-1,2,4-triazin- 5(4H)-ones and cyclic ketones under acidic conditions leads to the formation of zwitterion derivatives of 5,6,7,8,9,10,11,12-octahydro-[1,2,4]triazino[1,6- ƒ ]phenanthridine and 1,2,3,6,7,8-hexahydro-bicyclopenta[ b,d]pyrido[1,2- ƒ ][1,2,4]triazine.