A novel route to tetracyclic fused tetrazines and thiadiazines

The reaction between 3‐amino‐2,3‐dihydro‐7,9‐dimethyl‐2‐thioxo‐pyrido[3′,2′:4,5]thieno[3,2‐d]‐pyrimidin‐4(1H)‐one 4 or its 2‐methylthio derivative 5 with hydrazonoyl halides 6 in dioxane in the presence of triethylamine under reflux has followed heterocyclization reaction to yield pyrido[3″,2″:4′,5′]‐thieno[3′,2′:4,5]pyrimido[2,1‐c][1,2,4,5]tetrazin‐6(4H)‐ones 9. On the other hand, reaction of compound 4 with hydrazonoyl halides 6 in sodium ethoxide at room temperature led to formation of hydrazonothioate compounds 10. The latter on treatment with glacial acetic acid produced tetracyclic compounds, namely 2‐arylhydrazonopyrido[3″,2″:4′,5′]thieno [3′,2′:4,5]pyrimido[2,1‐b][1,3,4]thiadiazinones 11. An alternative method was carried out to prove the structure of product 11. The mechanism of the reaction under study was proposed and the products were screened for their biological activity.