Nitration of 5,11-dihydroindolo[3,2-b]carbazoles and synthetic applications of their nitro-substituted derivatives

A new general approach to double nitration of 6,12-di(hetero)aryl-substituted and 6,12-unsubstituted 5,11-dialkyl-5,11-dihydroindolo[3,2-b]carbazoles by acetyl nitrate has been developed to obtain their 2,8-dinitro and 6,12-dinitro derivatives, respectively. A formation of mono-nitro derivatives (at C-2 or C-6) from the same indolo[3,2-b]carbazoles has also been observed in several cases. Reduction of 2-nitro and 2,8-dinitro derivatives with zinc powder and hydrochloric acid has afforded 2-amino- and 2,8-diamino-substituted indolo[3,2-b]carbazoles, while reduction of 6,12-dinitro derivatives under similar reaction conditions has been accompanied by denitrohydrogenation of the latter compounds into 6,12-unsubstituted indolo[3,2-b]carbazoles. Formylation of 6,12-dinitro derivatives has proved to occur only at C-2, while bromination of these compounds has taken place at both C-2 and C-8 of indolo[3,2-b]carbazole scaffold. Moreover, 6,12-dinitro-substituted indolo[3,2-b]carbazoles have been modified by the reactions with S- and N-nucleophiles. Notably, the treatment of 6,12-dinitro compounds with potassium thiolates has resulted in the displacement of both nitro groups, unlike potassium salts of indole or carbazole, which have caused substitution of only one nitro group

A new and convenient synthetic way to 2-substituted thieno[2,3-b]indoles

Abstract A short and robust approach for the synthesis of 2-(hetero)aryl substituted thieno [2,3-b]indoles from easily available 1-alkylisatins and acetylated (hetero)arenes has been advanced. The two-step procedure includes the "aldol-crotonic" type of condensation of the starting materials, followed by treatment of the intermediate 3-(2-oxo-2-(hetero)arylethylidene)indolin-2-ones with Lawesson's reagent. The latter process involves two sequential reactions, namely reduction of the C=C ethylidene double bond of the intermediate indolin-2-ones followed by the Paal-Knorr cyclization, thus affording tricyclic thieno [2,3-b]indoles. 100