American Journal of Physical Chemistry

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Solvent Effects on the Kinetics of the Dakin-West Reaction

Received: 21 November 2016    Accepted: 05 December 2016    Published: 12 January 2017
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Abstract

The rate of the Dakin-West reaction have been investigated in Me2SO, THF and CH3CN at the temperature range (55–70) are reported. First order rate constants were obtained in each case. A Bronsted slope was found to be equal -0.0277 indicates that the transition state is very reactant-like and the proton has barely moved. Further, the solvent effect was considered from two points of mechanistic view: the thermodynamic transfer function of Me2SO to CH3CN and THF where the rate was found to be fast in Me2SO and slow in THF and CH3CN and the Kirkwood-Buff preferential solvation with aqueous Me2SO, CH3CN and THF. The techniques supported the proposed transition state structure.

DOI 10.11648/j.ajpc.20160506.13
Published in American Journal of Physical Chemistry (Volume 5, Issue 6, December 2016)
Page(s) 118-127
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This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Dakin-West Reaction, Kirkwood-Buff Theory, Azlactone, Thermodynamic Transfer Function, Solvent Effect, Bronsted Plot, Activity Coefficient

References
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[2] G. H. Cleland and Neiman (1949). Some observation on the Dakin – West Reaction. J. Am Chem. Soc. 71: 841.
[3] G. L. Buchana (1988) The Dakin –West Reaction. Chem. Soc. Rev. 17: 91.
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[16] R. Knorr and R. Huisgen (1970) Mechanism of the Dakin –West reaction. 1. Reaction of secondary N-acylamino acid with acetic anhydride. Chem. Ber. 103: 2598.
[17] R. Knorr and R. Huisgen (1971) Mechanism of the Dakin –West reaction. 111. Course of ring opening during the Dakin – West reaction of an oxazoline – 5 olate. Chem. Ber. 104: 3621.
[18] R. Knorr and G. K. Staudinger (1971) Mechanism of the Dakin –West reaction. 11. Acylation of Oxazoline – 5 –ones by carboxylic anhydride-pyridine. Chem. Ber. 104: 3633.
[19] E. Tomila and M. Murto (1963) the influence of the solvent on reaction velocity, XXIV. The acid hydrolysis of ethyl acetate in dimethyl sulphoxide – water mixture. Acta. Chem. Scand. 17: 1943.
[20] E. Tomila and M. Savolainen (1966) The Influence of the Solvent on Reaction Velocity. XXXI. The Reaction between Benzyl Chlorides and Methoxide Ion in Dimethyl Sulphoxide-Methanol Mixtures. Acta. Chem. Scand. 20: 946.
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Author Information
  • Department of Chemistry, College of Science and Home Economic, Bisha University, Bisha, Saudi Arabia; Departmen of Chemistry, College of Science and Education, University of West Kurdofan, EL Nuhud, Sudan

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    Ayman Abdelaziz Osman. (2017). Solvent Effects on the Kinetics of the Dakin-West Reaction. American Journal of Physical Chemistry, 5(6), 118-127. https://doi.org/10.11648/j.ajpc.20160506.13

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    Ayman Abdelaziz Osman. Solvent Effects on the Kinetics of the Dakin-West Reaction. Am. J. Phys. Chem. 2017, 5(6), 118-127. doi: 10.11648/j.ajpc.20160506.13

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    AMA Style

    Ayman Abdelaziz Osman. Solvent Effects on the Kinetics of the Dakin-West Reaction. Am J Phys Chem. 2017;5(6):118-127. doi: 10.11648/j.ajpc.20160506.13

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  • @article{10.11648/j.ajpc.20160506.13,
      author = {Ayman Abdelaziz Osman},
      title = {Solvent Effects on the Kinetics of the Dakin-West Reaction},
      journal = {American Journal of Physical Chemistry},
      volume = {5},
      number = {6},
      pages = {118-127},
      doi = {10.11648/j.ajpc.20160506.13},
      url = {https://doi.org/10.11648/j.ajpc.20160506.13},
      eprint = {https://download.sciencepg.com/pdf/10.11648.j.ajpc.20160506.13},
      abstract = {The rate of the Dakin-West reaction have been investigated in Me2SO, THF and CH3CN at the temperature range (55–70) are reported. First order rate constants were obtained in each case. A Bronsted slope was found to be equal -0.0277 indicates that the transition state is very reactant-like and the proton has barely moved. Further, the solvent effect was considered from two points of mechanistic view: the thermodynamic transfer function of Me2SO to CH3CN and THF where the rate was found to be fast in Me2SO and slow in THF and CH3CN and the Kirkwood-Buff preferential solvation with aqueous Me2SO, CH3CN and THF. The techniques supported the proposed transition state structure.},
     year = {2017}
    }
    

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    JF  - American Journal of Physical Chemistry
    JO  - American Journal of Physical Chemistry
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    AB  - The rate of the Dakin-West reaction have been investigated in Me2SO, THF and CH3CN at the temperature range (55–70) are reported. First order rate constants were obtained in each case. A Bronsted slope was found to be equal -0.0277 indicates that the transition state is very reactant-like and the proton has barely moved. Further, the solvent effect was considered from two points of mechanistic view: the thermodynamic transfer function of Me2SO to CH3CN and THF where the rate was found to be fast in Me2SO and slow in THF and CH3CN and the Kirkwood-Buff preferential solvation with aqueous Me2SO, CH3CN and THF. The techniques supported the proposed transition state structure.
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