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Kinetics of the [4+2] cycloaddition of cyclopentadiene with (E)-2-aryl-1-cyano-1-nitroethenes.

Jasiński R, Kwiatkowska M, Barański A - Monatsh. Chem. (2012)

Bottom Line: The electrophilicity of (E)-2-aryl-1-cyano-1-nitroethenes is not sufficient to induce a zwitterionic course of their [4+2] cycloaddition to cyclopentadiene.The one-step mechanism of these reactions is indicated by the activation parameters, and the substituent and solvent effects on the reaction.

View Article: PubMed Central - PubMed

Affiliation: Institute of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland.

ABSTRACT

Abstract: The electrophilicity of (E)-2-aryl-1-cyano-1-nitroethenes is not sufficient to induce a zwitterionic course of their [4+2] cycloaddition to cyclopentadiene. The one-step mechanism of these reactions is indicated by the activation parameters, and the substituent and solvent effects on the reaction.

No MeSH data available.


Plot of log k versus Reichardt–Dimroth ET(30) constants for the [4+2] cycloaddition of cyclopentadiene with (E)-2-(p-methoxycarbonylphenyl)-1-cyano-1-nitroethene (2g) (at 25 °C)
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Fig2: Plot of log k versus Reichardt–Dimroth ET(30) constants for the [4+2] cycloaddition of cyclopentadiene with (E)-2-(p-methoxycarbonylphenyl)-1-cyano-1-nitroethene (2g) (at 25 °C)

Mentions: To obtain a quantitative description of the solvent effect on the reaction rate, we studied correlations between substrate reactivity and the solvent polarity constants such as dielectric constant ε, dipole moment μ, Berson constant Ω, and Reichardt-Dimroth ET(30) constant [18, 19]. The best linear correlations were obtained for the ET(30) constants (Eqs. 5, 6) (Fig. 2).5\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ \log k_{\text{A}} = 0.09 \cdot E_{\text{T}} - 6.08\quad (R = 0.987) $$\end{document}6\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ \log k_{\text{B}} = 0.08 \cdot E_{\text{T}} - 4.76\quad (R = 0.994) $$\end{document}Fig. 2


Kinetics of the [4+2] cycloaddition of cyclopentadiene with (E)-2-aryl-1-cyano-1-nitroethenes.

Jasiński R, Kwiatkowska M, Barański A - Monatsh. Chem. (2012)

Plot of log k versus Reichardt–Dimroth ET(30) constants for the [4+2] cycloaddition of cyclopentadiene with (E)-2-(p-methoxycarbonylphenyl)-1-cyano-1-nitroethene (2g) (at 25 °C)
© Copyright Policy
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4495029&req=5

Fig2: Plot of log k versus Reichardt–Dimroth ET(30) constants for the [4+2] cycloaddition of cyclopentadiene with (E)-2-(p-methoxycarbonylphenyl)-1-cyano-1-nitroethene (2g) (at 25 °C)
Mentions: To obtain a quantitative description of the solvent effect on the reaction rate, we studied correlations between substrate reactivity and the solvent polarity constants such as dielectric constant ε, dipole moment μ, Berson constant Ω, and Reichardt-Dimroth ET(30) constant [18, 19]. The best linear correlations were obtained for the ET(30) constants (Eqs. 5, 6) (Fig. 2).5\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ \log k_{\text{A}} = 0.09 \cdot E_{\text{T}} - 6.08\quad (R = 0.987) $$\end{document}6\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ \log k_{\text{B}} = 0.08 \cdot E_{\text{T}} - 4.76\quad (R = 0.994) $$\end{document}Fig. 2

Bottom Line: The electrophilicity of (E)-2-aryl-1-cyano-1-nitroethenes is not sufficient to induce a zwitterionic course of their [4+2] cycloaddition to cyclopentadiene.The one-step mechanism of these reactions is indicated by the activation parameters, and the substituent and solvent effects on the reaction.

View Article: PubMed Central - PubMed

Affiliation: Institute of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, Poland.

ABSTRACT

Abstract: The electrophilicity of (E)-2-aryl-1-cyano-1-nitroethenes is not sufficient to induce a zwitterionic course of their [4+2] cycloaddition to cyclopentadiene. The one-step mechanism of these reactions is indicated by the activation parameters, and the substituent and solvent effects on the reaction.

No MeSH data available.