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Kinetic and equilibrium study of the deprotonation of 4-nitrophenyl[bis(ethylsulphonyl)]methane by organic bases in acetonitrile in the presence of common cation BH+ and tetrabutylammonium perchlorate

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Central European Journal of Chemistry

Abstract

The results of kinetic and equilibrium experiments with the set of reaction of proton abstraction from 4-nitrophenyl[bis(ethylsulphonyl)]methane in acetonitrile are reported. Two strong organic bases are used: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD).

The rates of proton transfer reaction have been measured by T-jump method in the presence of perchlorate of the appropriate base as a common cation BH+ and supporting electrolyte-tetrabutylammonium perchlorate (TBAP) in the temperature range between 20–40°C are: k H =1.32×107−2.00×107 and 2.82×107−4.84×107 dm 3mol−1s−1 for MTBD and TBD respectively. The enthalpies of activation ΔH ≠ MTBD =13.5 and ΔH ≠ TBD =18.1 kJmol−1. The entropies of activation are negative: ΔS ≠ MTBD =−62.3 and ΔS ≠ TBD =−40.3 Jmol−1K−1.

The change of the absorbance of the anion of 4-nitrophenyl[bis9ethylsulphonyl)]methane at the temperature 25°C in the presence of common cation BH+ gives the equilibrium constants K=705 and 906 M−1 for MTBD and TBD respectively.

Kinetic and equilibrium results are discussed. The possible mechanism of proton transfer reaction between 4-nitrophenyl[bis(ethylsulphonyl)]methane and cyclic organic bases: MTBD and TBD in acetonitrile is proposed.

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  1. Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780, Poznań, Poland

    Iwona Binkowska & Arnold Jarczewski

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  1. Iwona Binkowska
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Binkowska, I., Jarczewski, A. Kinetic and equilibrium study of the deprotonation of 4-nitrophenyl[bis(ethylsulphonyl)]methane by organic bases in acetonitrile in the presence of common cation BH+ and tetrabutylammonium perchlorate. cent.eur.j.chem. 2, 648–659 (2004). https://doi.org/10.2478/BF02482728

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