Ацилювання індолілзаміщених β-кетонітрилів. Шлях до нових похідних індоло[2,3-c]пірилію та β-карболіну

N. M. Bogdan; S. L. Bogza; Yu. A. Nikolyukin

doi:10.24959/ophcj.20.206021

Authors

N. M. Bogdan Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0002-6522-1694
S. L. Bogza Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0002-1274-3720
Yu. A. Nikolyukin PortaScience Inc., United States

DOI:

https://doi.org/10.24959/ophcj.20.206021

Keywords:

indole, ketonitrile, pyrilium, recyclization, β-carboline

Abstract

Aim. To synthesize 4-cyanoindolo[2,3-c]pyrilium salts and examine their reactivity towards N-nucleophiles.

Results and discussion. The acylation reaction of 2-(indolyl-3)-2-aroylacetonitriles under acid catalysis conditions was studied. 4-Cyanoindolo[2,3-c]pyrillium borofluorides were obtained, and ketonitrile enolacylates were isolated as by-products of the reaction. Treatment of the 4-cyanoindolo[2,3-c]pyrilium salts with ammonia led to 4-cyano-β-carbolines while the interaction of the salts with hydrazine hydrate resulted in formation of pyrazolo[3’,4’:5,6]pyrido[3,4‑b]indoles – derivatives of a new heterocyclic system. The latter are formed via recyclization involving the pyran ring and the cyano group.

Experimental part. Upon the treatment of 2-(indolyl-3)-2-aroylacetonitriles with acetic anhydride/tetrafluoroboric acid mixture, the acylation of the indole fragment in position 2 was followed by cyclization, resulting in formation of 4-сyanoindolo[2,3-c]pyrilium salts. The reactivity of the pyrylium salts was studied on the examples of their interaction with N-nucleophiles – ammonia and hydrazine hydrate. The structure of the compounds synthesized was confirmed by ¹H NMR, IR spectroscopy and elemental analysis.

Conclusions. It has been found that moderate yields of 4-сyanoindolo[2,3-c]pyrilium salts are the result of competing acylation of the hydroxyl group of enol ketonitrile, which blocks the pyran ring formation. Recylization of the salts with ammonia leads to 4-cyano-β-carbolines. Transformation of the pyran ring with hydrazine hydrate proceeds with the participation of the cyano group as a tandem reaction with formation of pyrazolo[3’,4’:5,6]pyrido[3,4-b]indoles.

Received: 22.06.2020
Revised: 03.10.2020
Accepted: 23.10.2020

Supporting Agencies

The theme of the NAS of Ukraine "Minimalistic design of synthetic routes for synthesis of azoloazines
azolo(azino)diazepines and other polycondensed heterocyclic systems» (№ 0116U008794
2016 – 2021 years)

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