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Vol. 26 No. 23 (2014)

Copyright (c) 2014 Mahmoud F. Ibrahim1, Asma A.A. Al-Karewi1, Sherine N. Khattab1, Ezzat A. Hamed1, Ayman El-Faham1

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This work is licensed under a Creative Commons Attribution 4.0 International License.

Aminolysis of Isatin and N-Acetyl Isatin in Acetonitrile and Mixed Acetonitrile-Water Solvents

https://doi.org/10.14233/ajchem.2014.16968
Mahmoud F. Ibrahim1
1Department of Chemistry, Faculty of Science, Alexandria University, Ibrahimia 21321, P.O. Box 426, Alexandria, Egypt 2Department of Chemistry, Faculty of Science, Beirut Arab University, Beiurt, Lebanon 3Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, 11451 Riyadh, Kingdom of Saudi Arabia 4Institute for Research in Biomedicine, Barcelona Science Park, Baldiri Reixac 10, 08028-Barcelona, Spain *Corresponding authors: Tel: +961 71244851; E-mail: ezzatah2@hotmail.com (E. A. Hamed); Fax: +2 03 5771399; Tel.: +2 0122 3140924; E-mail: aymanel_faham@hotmail.com (A. El- Faham)
Asma A.A. Al-Karewi1
1Department of Chemistry, Faculty of Science, Alexandria University, Ibrahimia 21321, P.O. Box 426, Alexandria, Egypt 2Department of Chemistry, Faculty of Science, Beirut Arab University, Beiurt, Lebanon 3Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, 11451 Riyadh, Kingdom of Saudi Arabia 4Institute for Research in Biomedicine, Barcelona Science Park, Baldiri Reixac 10, 08028-Barcelona, Spain *Corresponding authors: Tel: +961 71244851; E-mail: ezzatah2@hotmail.com (E. A. Hamed); Fax: +2 03 5771399; Tel.: +2 0122 3140924; E-mail: aymanel_faham@hotmail.com (A. El- Faham)
Sherine N. Khattab1
1Department of Chemistry, Faculty of Science, Alexandria University, Ibrahimia 21321, P.O. Box 426, Alexandria, Egypt 2Department of Chemistry, Faculty of Science, Beirut Arab University, Beiurt, Lebanon 3Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, 11451 Riyadh, Kingdom of Saudi Arabia 4Institute for Research in Biomedicine, Barcelona Science Park, Baldiri Reixac 10, 08028-Barcelona, Spain *Corresponding authors: Tel: +961 71244851; E-mail: ezzatah2@hotmail.com (E. A. Hamed); Fax: +2 03 5771399; Tel.: +2 0122 3140924; E-mail: aymanel_faham@hotmail.com (A. El- Faham)
Ezzat A. Hamed1
1Department of Chemistry, Faculty of Science, Alexandria University, Ibrahimia 21321, P.O. Box 426, Alexandria, Egypt 2Department of Chemistry, Faculty of Science, Beirut Arab University, Beiurt, Lebanon 3Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, 11451 Riyadh, Kingdom of Saudi Arabia 4Institute for Research in Biomedicine, Barcelona Science Park, Baldiri Reixac 10, 08028-Barcelona, Spain *Corresponding authors: Tel: +961 71244851; E-mail: ezzatah2@hotmail.com (E. A. Hamed); Fax: +2 03 5771399; Tel.: +2 0122 3140924; E-mail: aymanel_faham@hotmail.com (A. El- Faham)
Ayman El-Faham1
1Department of Chemistry, Faculty of Science, Alexandria University, Ibrahimia 21321, P.O. Box 426, Alexandria, Egypt 2Department of Chemistry, Faculty of Science, Beirut Arab University, Beiurt, Lebanon 3Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, 11451 Riyadh, Kingdom of Saudi Arabia 4Institute for Research in Biomedicine, Barcelona Science Park, Baldiri Reixac 10, 08028-Barcelona, Spain *Corresponding authors: Tel: +961 71244851; E-mail: ezzatah2@hotmail.com (E. A. Hamed); Fax: +2 03 5771399; Tel.: +2 0122 3140924; E-mail: aymanel_faham@hotmail.com (A. El- Faham)

Corresponding Author(s) : Mahmoud F. Ibrahim1

Asian Journal of Chemistry, Vol. 26 No. 23 (2014)

Abstract

The reactions of N-acetyl isatin and N-propionyl isatin with morpholine, piperazine and diethylamine in acetonitrile underwent nucleophilic substitution reactions at the amide linkage with ring opening process to give N-[2-(2-amino-2-oxo-acetyl)phenyl]acetamide derivatives and N-[2-(2-amino-2-oxoacetyl)phenyl]propionamide derivatives, respectively. The rate constants of the titled reactions were studied spectrophotometerically in pure acetonitrile and acetonitrile-water mixed solvent. The reactions in pure acetonitrile obeyed third order kinetics. The activation parameters suggest that the mechanism of the reaction proceeds by parallel specific base and dimer mechanisms depending on temperature and the nature of amine. The reaction of isatin with piperazine in acetonitrile-water mixed solvent passes through formation of solvated intermediate which in turn gives zwitterionic ion intermediate that leads to the final product in a slow step. The nonlinear plots of log kN versus 1/D of the binary solvent as well as the plot of log kN versus XH2O, indicate a specific solvation. The plot of log kN versus log [H2O] gives the number of water molecules (n) contaminated in the transition state. The inversely proportional correlation between ENT and log kA values agrees with the formation of solvated zwitterionic (tetrahedral) intermediates in the rate determined step. The application of multiparameter approach of a, b and p* indicates that the rate of the reaction is influenced by both specific and nonspecific solute-solvent interactions.

Keywords

Isatin N-acetyl isatin Kinetics Morpholine Piperazine Diethylamine.
F. Ibrahim1, M., A.A. Al-Karewi1, A., N. Khattab1, S., A. Hamed1, E., & El-Faham1, A. (2014). Aminolysis of Isatin and N-Acetyl Isatin in Acetonitrile and Mixed Acetonitrile-Water Solvents. Asian Journal of Chemistry, 26(23), 8029–8038. https://doi.org/10.14233/ajchem.2014.16968
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