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Comparison of kinetic and thermodynamic parameters of reaction of individual conformers of α-substituted β-ethoxyvinyl trifluoromethyl ketones with secondary amines

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Abstract

The kinetic and thermodynamic parameters of the reaction of three most possible conformers (viz. E-s-E-s-E-trans, E-s-Z-s-E-trans, and E-s-Z-s-E-gosh) of α-substituted β-ethoxyvinyl trifluoromethyl ketones C2H5O–CH=CR-COCF3 (I–III) (I: R = H; II: R = F; III: R2 = CH3) with two secondary amines, namely diethyl amine (2a) and bis-(methoxyethyl) amine (2b), was studied in carbon tetrachloride as solvent. The details of appropriate enaminoketone formation are discussed in terms of an addition–elimination substitution. It is shown the limiting step of the reaction of all conformers presented in significant quantities, to be the formation of zwitterion intermediate. At high amine concentrations the third-order rate coefficient appears in reaction rate equation as a consequence of catalyzed route of the intermediate decomposition. The reaction of all three conformers has low ΔH≠ and high negative ΔS≠ values owing to highly polar zwitterion formation as the intermediate.

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Main results of spacial and electronic investigations of enones I-II are represented in Table 3, whereas detailed data are listed in supplementary materials

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Authors and Affiliations

  1. Institute of Bioorganic and Petrochemistry, National Academy of Scirnces of Ukraine, Akademika Kukhara street, 1, Kiev, 02094, Ukraine

    Sergey I. Vdovenko & Igor I. Gerus

  2. Faculty of Chemistry, University of Wroclaw, Jolio-Curie 14, 50-383, Wroclaw, Poland

    Magdalena Pagacz-Kostrzewa & Maria Wierzejewska

Authors
  1. Sergey I. Vdovenko
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  2. Igor I. Gerus
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  3. Magdalena Pagacz-Kostrzewa
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  4. Maria Wierzejewska
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Correspondence to Sergey I. Vdovenko.

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Vdovenko, S.I., Gerus, I.I., Pagacz-Kostrzewa, M. et al. Comparison of kinetic and thermodynamic parameters of reaction of individual conformers of α-substituted β-ethoxyvinyl trifluoromethyl ketones with secondary amines. Reac Kinet Mech Cat 137, 719–736 (2024). https://doi.org/10.1007/s11144-024-02578-1

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