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Synthesis 2006(14): 2357-2370  
DOI: 10.1055/s-2006-942433
PAPER
© Georg Thieme Verlag Stuttgart · New York

Substituted 4-(3-Cyanopyridin-2-ylthio)acetoacetates: New Convenient Reagents for the Synthesis of Heterocycles

Lyudmila Rodinovskaya*, Anatoliy Shestopalov, Anna Gromova, Alexander Shestopalov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russia
e-Mail: shchem@dol.ru;
Further Information

Publication History

Received 31 January 2006
Publication Date:
26 June 2006 (online)

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Abstract

Polyfunctional 4-(3-cyanopyridin-2-ylthio)acetoacetates were used in the synthesis of 4-hydroxy-1H-thieno[2,3-b:4,5-b]dipyridin-2-ones. The latter were used in reactions with arylidene­malononitriles or in three-component reactions with aldehydes and malononitrile to give 2-amino-4-aryl-3-cyano-5-oxo-5,6-dihydro-4H-pyrano[2,3-d]pyrido[3′,2′:4,5]thieno[3,2-b]pyridines. Utilizing 4-(3-cyanopyridin-2-ylthio)acetoacetates and arylidenemalononitriles or aldehydes and malononitrile, we developed a method for the synthesis of substituted 3-alkoxycarbonyl-6-amino-4-aryl-2-(3-cyanopyridin-2-ylthiomethyl)-4H-pyrans. Reactions of substituted 4-(3-cyanopyridin-2-ylthio)acetoacetates with hydrazine hydrate yielded substituted 3-hydroxypyrazoles, which were further used for the preparation of 6-amino-4-aryl-5-cyano-3-(pyrid-2-ylthio­methylene)-2,4-dihydropyrano[2,3-c]pyrazoles. Analogously, ethyl 4-(3-cyano-1,4-dihydropyridin-2-ylthio)acetoacetates were used for the synthesis of substituted 2-amino-4H-pyrans.

Key words

2-amino-4H-pyrans - thienopyridines - 4-(3-cyanopyridin-2-ylthio)acetoacetates - pyranopyridines - multi-component reactions

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The X-ray diffraction study was performed by Doct. Sci. (Chem.) V. S. Sergienko at the N. S. Kurnakov Institute of General and Inorganic Chemistry (Moscow).