A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts

Ismail Althagafi; Ahmed Fawzy

doi:doi:10.11648/j.ajhc.20160201.11

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A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts

Ismail Althagafi, Ahmed Fawzy

Published in American Journal of Heterocyclic Chemistry (Volume 2, Issue 1)

Received: 16 September 2016 Accepted: 31 October 2016 Published: 21 November 2016

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Abstract

Oxidation of methylaminopyrazole formamidine (MAPF) by permanganate ion was studied spectrophotometrically in neutral medium in the presence of phosphate buffer solution. The stoichiometry of the reaction was found to be 3: 2 (MAPF: MnO ₄^-). The oxidation reaction showed a first order kinetics with respect to [MnO₄^-] and a fractional-first order dependence with respect to [MAPF]. Addition of small amounts of some metal ions increased the oxidation rate and the order of catalytic efficiency was: Ag(I) > Cu(II) > Al(III). The suggested oxidation mechanism involves formation of a 1:1 intermediate complex between permanganate ion and MAPF. The formed complex decomposes in the rate-determining step to yield a free radical derived from MAPF and an intermediate Mn(VI). The free radical is attacked by Mn(VI) species to give rise to the final oxidation products which were identified by both spectroscopic and chemical tools as methylaminopyrazole, dimethylamine and carbon dioxide. The rate-law expression was deduced and the reaction constants involved in the different steps of the suggested mechanism were evaluated. The activation parameters of the rate constant of the slow step along with the thermodynamic quantities of the formation constant of the intermediate complex were evaluated and discussed.

Published in	American Journal of Heterocyclic Chemistry (Volume 2, Issue 1)
DOI	10.11648/j.ajhc.20160201.11
Page(s)	1-7
Creative Commons	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), 2016. Published by Science Publishing Group

Keywords

Methylaminopyrazole Formamidine, Oxidation, Permanganate, Kinetics, Mechanism

References

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Ismail Althagafi, Ahmed Fawzy. (2016). A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts. American Journal of Heterocyclic Chemistry, 2(1), 1-7. https://doi.org/10.11648/j.ajhc.20160201.11

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ACS Style

Ismail Althagafi; Ahmed Fawzy. A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts. Am. J. Heterocycl. Chem. 2016, 2(1), 1-7. doi: 10.11648/j.ajhc.20160201.11

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AMA Style

Ismail Althagafi, Ahmed Fawzy. A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts. Am J Heterocycl Chem. 2016;2(1):1-7. doi: 10.11648/j.ajhc.20160201.11

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@article{10.11648/j.ajhc.20160201.11,
  author = {Ismail Althagafi and Ahmed Fawzy},
  title = {A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts},
  journal = {American Journal of Heterocyclic Chemistry},
  volume = {2},
  number = {1},
  pages = {1-7},
  doi = {10.11648/j.ajhc.20160201.11},
  url = {https://doi.org/10.11648/j.ajhc.20160201.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajhc.20160201.11},
  abstract = {Oxidation of methylaminopyrazole formamidine (MAPF) by permanganate ion was studied spectrophotometrically in neutral medium in the presence of phosphate buffer solution. The stoichiometry of the reaction was found to be 3: 2 (MAPF: MnO 4-). The oxidation reaction showed a first order kinetics with respect to [MnO4-] and a fractional-first order dependence with respect to [MAPF]. Addition of small amounts of some metal ions increased the oxidation rate and the order of catalytic efficiency was: Ag(I) > Cu(II) > Al(III). The suggested oxidation mechanism involves formation of a 1:1 intermediate complex between permanganate ion and MAPF. The formed complex decomposes in the rate-determining step to yield a free radical derived from MAPF and an intermediate Mn(VI). The free radical is attacked by Mn(VI) species to give rise to the final oxidation products which were identified by both spectroscopic and chemical tools as methylaminopyrazole, dimethylamine and carbon dioxide. The rate-law expression was deduced and the reaction constants involved in the different steps of the suggested mechanism were evaluated. The activation parameters of the rate constant of the slow step along with the thermodynamic quantities of the formation constant of the intermediate complex were evaluated and discussed.},
 year = {2016}
}

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TY  - JOUR
T1  - A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts
AU  - Ismail Althagafi
AU  - Ahmed Fawzy
Y1  - 2016/11/21
PY  - 2016
N1  - https://doi.org/10.11648/j.ajhc.20160201.11
DO  - 10.11648/j.ajhc.20160201.11
T2  - American Journal of Heterocyclic Chemistry
JF  - American Journal of Heterocyclic Chemistry
JO  - American Journal of Heterocyclic Chemistry
SP  - 1
EP  - 7
PB  - Science Publishing Group
SN  - 2575-5722
UR  - https://doi.org/10.11648/j.ajhc.20160201.11
AB  - Oxidation of methylaminopyrazole formamidine (MAPF) by permanganate ion was studied spectrophotometrically in neutral medium in the presence of phosphate buffer solution. The stoichiometry of the reaction was found to be 3: 2 (MAPF: MnO 4-). The oxidation reaction showed a first order kinetics with respect to [MnO4-] and a fractional-first order dependence with respect to [MAPF]. Addition of small amounts of some metal ions increased the oxidation rate and the order of catalytic efficiency was: Ag(I) > Cu(II) > Al(III). The suggested oxidation mechanism involves formation of a 1:1 intermediate complex between permanganate ion and MAPF. The formed complex decomposes in the rate-determining step to yield a free radical derived from MAPF and an intermediate Mn(VI). The free radical is attacked by Mn(VI) species to give rise to the final oxidation products which were identified by both spectroscopic and chemical tools as methylaminopyrazole, dimethylamine and carbon dioxide. The rate-law expression was deduced and the reaction constants involved in the different steps of the suggested mechanism were evaluated. The activation parameters of the rate constant of the slow step along with the thermodynamic quantities of the formation constant of the intermediate complex were evaluated and discussed.
VL  - 2
IS  - 1
ER  -

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Author Information

Ismail Althagafi

Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Ahmed Fawzy

Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt

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APA Style

Ismail Althagafi, Ahmed Fawzy. (2016). A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts. American Journal of Heterocyclic Chemistry, 2(1), 1-7. https://doi.org/10.11648/j.ajhc.20160201.11

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ACS Style

Ismail Althagafi; Ahmed Fawzy. A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts. Am. J. Heterocycl. Chem. 2016, 2(1), 1-7. doi: 10.11648/j.ajhc.20160201.11

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AMA Style

Ismail Althagafi, Ahmed Fawzy. A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts. Am J Heterocycl Chem. 2016;2(1):1-7. doi: 10.11648/j.ajhc.20160201.11

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@article{10.11648/j.ajhc.20160201.11,
  author = {Ismail Althagafi and Ahmed Fawzy},
  title = {A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts},
  journal = {American Journal of Heterocyclic Chemistry},
  volume = {2},
  number = {1},
  pages = {1-7},
  doi = {10.11648/j.ajhc.20160201.11},
  url = {https://doi.org/10.11648/j.ajhc.20160201.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajhc.20160201.11},
  abstract = {Oxidation of methylaminopyrazole formamidine (MAPF) by permanganate ion was studied spectrophotometrically in neutral medium in the presence of phosphate buffer solution. The stoichiometry of the reaction was found to be 3: 2 (MAPF: MnO 4-). The oxidation reaction showed a first order kinetics with respect to [MnO4-] and a fractional-first order dependence with respect to [MAPF]. Addition of small amounts of some metal ions increased the oxidation rate and the order of catalytic efficiency was: Ag(I) > Cu(II) > Al(III). The suggested oxidation mechanism involves formation of a 1:1 intermediate complex between permanganate ion and MAPF. The formed complex decomposes in the rate-determining step to yield a free radical derived from MAPF and an intermediate Mn(VI). The free radical is attacked by Mn(VI) species to give rise to the final oxidation products which were identified by both spectroscopic and chemical tools as methylaminopyrazole, dimethylamine and carbon dioxide. The rate-law expression was deduced and the reaction constants involved in the different steps of the suggested mechanism were evaluated. The activation parameters of the rate constant of the slow step along with the thermodynamic quantities of the formation constant of the intermediate complex were evaluated and discussed.},
 year = {2016}
}

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TY  - JOUR
T1  - A Study of the Kinetic and Mechanism of Oxidation of Pyrazole Derivative by Permanganate Ion in Neutral Medium and the Effect of Metal Ion Catalysts
AU  - Ismail Althagafi
AU  - Ahmed Fawzy
Y1  - 2016/11/21
PY  - 2016
N1  - https://doi.org/10.11648/j.ajhc.20160201.11
DO  - 10.11648/j.ajhc.20160201.11
T2  - American Journal of Heterocyclic Chemistry
JF  - American Journal of Heterocyclic Chemistry
JO  - American Journal of Heterocyclic Chemistry
SP  - 1
EP  - 7
PB  - Science Publishing Group
SN  - 2575-5722
UR  - https://doi.org/10.11648/j.ajhc.20160201.11
AB  - Oxidation of methylaminopyrazole formamidine (MAPF) by permanganate ion was studied spectrophotometrically in neutral medium in the presence of phosphate buffer solution. The stoichiometry of the reaction was found to be 3: 2 (MAPF: MnO 4-). The oxidation reaction showed a first order kinetics with respect to [MnO4-] and a fractional-first order dependence with respect to [MAPF]. Addition of small amounts of some metal ions increased the oxidation rate and the order of catalytic efficiency was: Ag(I) > Cu(II) > Al(III). The suggested oxidation mechanism involves formation of a 1:1 intermediate complex between permanganate ion and MAPF. The formed complex decomposes in the rate-determining step to yield a free radical derived from MAPF and an intermediate Mn(VI). The free radical is attacked by Mn(VI) species to give rise to the final oxidation products which were identified by both spectroscopic and chemical tools as methylaminopyrazole, dimethylamine and carbon dioxide. The rate-law expression was deduced and the reaction constants involved in the different steps of the suggested mechanism were evaluated. The activation parameters of the rate constant of the slow step along with the thermodynamic quantities of the formation constant of the intermediate complex were evaluated and discussed.
VL  - 2
IS  - 1
ER  -

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