Ethyl 3-amino-4-chlorothieno[3,2-c]quinoline-2-carboxylate (4) is a versatile synthon, prepared by reacting an equimolar amount of 2,4-dichloroquinoline-3-carbonitrile (1) with ethyl mercaptoacetate (2). Ethyl 5-alkyl-5H-1-thia-3,5,6-triazaaceanfhrylene-2-carboxylates 9a-c, novel perianellated tetracyclic heteroaro-matics, were prepared by refluxing 4 with excess of primary amines 7a-c to yield the corresponding amino-thieno[3,2-c]quinolines 8a-c. Subsequent reaction with an excess of triethyl orthoformate (TEO) furnished 9a-c. Reaction of 4 with TEO in Ac2O at reflux, gave the simple acetylated compounds, thieno[3,2-c]-quinolines 12 and 13. Refluxing 4 with benzylamine (7d) gave 10, and subsequent treatment with TEO gave the tetracyclic compound 11. Refluxing 13 with an excess of alkylamines 7a-d gave the fhieno[3,2-c]quino-lines 15. Refluxing the aminothienoquinolines 8b with an excess of triethyl orthoacetate gave thieno[3,2-c]quinoline 17, while heating with Ac2O gave 18 and 19, with small amounts of 16. Reaction of 8a,b with ethyl chloroformate and phenylisothiocyanate generated the new 1-thia-3,5,6-triazaaceanthrylenes 20a,b and 21a,b, respectively. Diazotization of 8a-c afforded the novel tetracyclic ethyl 5-alkyl-5H-1-fhia-3,4,5,6-tetraazaaceanthrylene-2-carboxylates 22a-c in good yields.