Two-stage one-pot interaction of acyclic β-ketoesters, dmfdma and 2-cyanomethylbenzimidazole

doi:10.26565/2220-637X-2017-29-03

Mariia A. Vodolazhenko SSI “Institute for Single Crystals”, National Academy of Sciences of Ukraine https://orcid.org/0000-0002-4581-8549
Anastasia E. Mykhailenko SSI “Institute for Single Crystals”, National Academy of Sciences of Ukraine
Nikolay Yu. Gorobets SSI “Institute for Single Crystals”, National Academy of Sciences of Ukraine https://orcid.org/0000-0001-8089-4646
Sergey M. Desenko SSI “Institute for Single Crystals”, National Academy of Sciences of Ukraine

DOI: https://doi.org/10.26565/2220-637X-2017-29-03

Keywords: β-ketoester, 2-cyanomethylbenzimidazole, one-pot heterocyclization, DMFDMA, microwave irradiation

Abstract

A one-pot two-stage interaction of acyclic β-ketoesters, dimethylformamide dimethylacetal (DMFDMA) and 2-cyanomethylbenzimidazole was studied. Carried out under microwave irradiation in 2-propanol in the presence of piperidine, this transformation leads to the formation of 4-cyanobenzo[4,5]imidazo[1,2-α]pyridine-2-carboxylates, whereas at room temperature in methanol in the presence of sodium methylate 1-hydroxybenzo[4,5]imidazo[1,2-α]pyridine-4-carbonitriles are formed. Intermediate enamines initially formed from β-ketoesters and DMFDMA attack methylene group of 2-cyanomethylbenzimidazole followed by heterocyclizaton. In the presence of piperidine the benzimidazole nitrogen atom attacks the keto group of the β-ketoester fragment, whereas in the strong basic conditions cyclization occurs by the ester group.

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