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Three-Component Reaction of Dimethyl Malonate with α,β-Acetylenic Aldehydes and Amines. Synthesis of Push–Pull Buta-1,3-dienes

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Abstract

Three-component reaction of dimethyl malonate with α,β-acetylenic aldehydes and cyclic secondary amines (pyrrolidine, piperidine, morpholine, and piperazine) under mild conditions afforded dimethyl 2-(3-aminoprop-2-en-1-ylidene)malonates in 50–91% yields. The products were formed preferentially as E isomers, and the described reaction provides a convenient method for the synthesis of push–pull buta-1,3-dienes that are interesting as fluorescent, solvatochromic, and nonlinear optical materials and starting compounds in the synthesis of carbo- and heterocycles. A plausible reaction mechanism involves Knoevenage condensation of dimethyl malonate with α,β-acetylenic aldehyde to give dimethyl 2-(prop-2-yn-1-ylidene)malonate and subsequent nucleophilic addition of cyclic amine to the latter.

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ACKNOWLEDGMENTS

The authors thank K.V. Gordon for performing elemental analyses.

Funding

This study was performed under financial support by the Russian Foundation for Basic Research (project no. 20-33-80004/20).

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Authors and Affiliations

  1. Ufa State Petroleum Technological University, 450062, Ufa, Russia

    S. A. Sokov & S. S. Zlotskii

  2. Togliatti State University, 445020, Togliatti, Russia

    S. A. Sokov, I. S. Odin & A. A. Golovanov

Authors
  1. S. A. Sokov
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  2. I. S. Odin
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  3. S. S. Zlotskii
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  4. A. A. Golovanov
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Correspondence to A. A. Golovanov.

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Sokov, S.A., Odin, I.S., Zlotskii, S.S. et al. Three-Component Reaction of Dimethyl Malonate with α,β-Acetylenic Aldehydes and Amines. Synthesis of Push–Pull Buta-1,3-dienes. Russ J Org Chem 56, 1758–1763 (2020). https://doi.org/10.1134/S1070428020100140

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