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

• Authors: Iwona Binkowska , Arnold Jarczewski
• Languages of publication: EN

Abstracts

EN

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: kH=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 ΔHMTBD≠=13.5 and ΔHTBD≠=18.1 kJmol−1. The entropies of activation are negative: ΔSMTBD≠=−62.3 and ΔSTBD≠=−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.

Keywords

EN

proton transfer; carbon acid; T-jump method; TBD and MTBD bases; kinetics

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2004
• Volume: 2
• Issue: 4
• Pages: 648-659

Dates

published

1 - 12 - 2004

online

1 - 12 - 2004

Contributors

author

Iwona Binkowska

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

author

Arnold Jarczewski

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

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Identifiers

DOI

10.2478/BF02482728