Abstract
The kinetics of the oxidation of substituted 4-oxoacids by N-bromosaccharin (NBSac) has been studied in aqueous acetic acid medium at 30 °C. The reactions follow first-order kinetics in the 4-oxoacids, NBSA and H+. Variation in the ionic strength has no effect on the reaction rate. The order of reactivity among the studied 4-oxoacids is: 4-methoxy > 4-methyl > 4-phenyl > 4-H > 4-Cl > 4-Br > 3-NO2. The effect of changes in the electronic nature of the substrate revealed that there is a development of positive charge in the transition state. The activation parameters were computed from an Arrhenius plot. Based on the kinetic results, a suitable mechanism has been proposed. The mechanism involves the attack of the oxidizing species hypobromous acidium ion, (H2O+Br).
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References
Reddy, C.S., Manjari, P.S.: Kinetics and mechanism of acid bromate oxidation of substituted 4-oxoacids. Indian J. Chem. 49A, 418–424 (2010)
Gupta, M.-K., Rekha, L., Sharma, P.-K., Sharma, K., Sharma, V.-K.: Oxidation of glycolic acid by N-bromosaccharin–A kinetic and mechanistic study in presence and absence of cationic surfactant. Asian J. Chem. 18, 1340–1346 (2006)
Mohamed Farook, N.A.: Kinetics of oxidation of 4-oxo acids by N-bromosuccinimide in aqueous acetic acid medium. J. Iranian Chem. Soc. 3, 378–386 (2006)
Mohamed Farook, N.-A.: Kinetics of oxidation of 4-oxo acids by N-chlorosaccharin in aqueous acetic acid. J. Solution Chem. 36, 345–356 (2007)
Mohamed Farook, N.-A., Seyed Dameem, G.-A.: Kinetics of oxidation of 3-benzoylpropionic acid by N-chlorobenzamide in aqueous acetic acid medium. J. Chem. 8, 561–564 (2011)
Freeda Gnana Rani, D., Maria Pushparaj, F.-J., Alphones, I., Rangappa, K.-S.: Kinetics and mechanism of oxidation of 4-oxoacids by hexacyanoferrate(III) catalysed by Os(VIII). Indian J. Chem. 41B, 2153–2159 (2002)
Sikkandar, G.: Kinetics of oxidatative decarboxylation of β-benzoylpropionic acid by manganese(III) acetate. Asian J. Chem. 12, 1037–1040 (2000)
De Barry, E.B., Sanders, F.G.: The synthesis of some homologous naphthalenes. J. Chem. Soc. 434–437 (1933)
Fieser, L.F., Seligman, A.M.: 1′-Methyl- and 1′,10-dimethyl-1,2-benzanthracene. J. Am. Chem. Soc. 60, 170–176 (1938)
Vogel, A.I.: A Text Book of Practical Organic Chemistry. Longmans Green, London (1962)
Russell, R.R., Van der Werf, C.A.: The malonic ester synthesis with styrene oxide and with butadiene oxide. J. Am. Chem. Soc. 69, 11–13 (1947). doi:10.1021/ja01193a003
Hey, D.H., Wilkinson, R.: The preparation of 2-phenylnapthalene from diphenyl. J. Chem. Soc. 1030 (1940)
Chapman, N.B., Shorter, J.: Advances in linear free energy relationships. Plenum Press (1972)
Mohamed Farook, N.-A., Dameem, S.: Kinetics of oxidation of 3-benzoylpropionic acid by N-bromoacetamide in aqueous acetic acid medium. J. Chem. 8, 479–482 (2011)
Mohamed Farook, N.-A., Prabhkaran, R., Rahini, S., Senthil Kumar, R., Raja Mahendran, G., Gopala Krishnan, G.: Kinetics of oxidation of some amino acids by N-chlorosaccharin in aqueous acetic acid medium. J. Chem. 2, 127–131 (2004)
Vivekanandan, K., Nambi, K.: Kinetics and mechanistic study of amino acids by N-chloronicotinimide in acid medium. J. Indian Chem. Soc. 76, 198–202 (1999)
Mohamed Farook, N.-A., Alhaji, N.-M.-I.: Kinetics of oxidation of substituted γ-ketoacid by N-chlorosaccharin in aqueous acetic acid medium. Int. J. Chem. Sci. 2, 76–80 (2004)
Mohamed Farook, N.-A., Seyed Dameem, G.-A., Murugesan, A., Kanagaraj, M.: Kinetics of oxidation of some essential amino acids by N-chlorosaccharin in aqueous acetic acid medium. J. Chem. 2, 132–136 (2004)
Kothari, S., Agarwal, A., Banerji, K–.K.: Kinetics and mechanism of oxidation of primary alcohols by N-bromo-3-5-dinitrobenzamide. Indian J. Chem. 25A, 722–724 (1986)
Nath, M.-P., Banerji, K.-K.: Kinetics and mechanisms of the oxidation of methyl aryl ketones by acid permanganate. Aust. J. Chem. 29, 1939–1945 (1976)
Vanangamudi, G., Srinivasan, S.: Kinetic studies on the oxidation of some para and meta-substituted cinnamic acids by pyridinium bromochromate in the presence of oxalic acid (a co-oxidation study). J. Chem. 6, 920–927 (2009)
Gould, E.-S.: Mechanism and Structure in Organic Chemistry, pp. 181–185. Holt Riehart and Winston, New York (1964)
Richard Johnes, A.-Y.: Physical and Mechanistic Organic Chemistry. Cambridge University Press, New York (1984)
Ruff, F., Kucsman, A.: Mechanism of the oxidation of sulphides with sodium periodate. J. Chem. Soc. Perkin Trans. II, 683–688 (1985)
Cotton, F.-A., Wilkinson, G.: Advanced Inorganic Chemistry. John Wiley, 5th edn. (1988)
Greenwood, N-.N., Earnshaw, A.: Chemistry of the Elements, p. 1222. Pergamon Press, Oxford (1984)
Issacs, S.N.: Physical Organic Chemistry. Longman Scientific & Technical, New York (1987)
Leffler, J.-F., Grunwald, E.: Rates and Equilibrium of Organic Reactions. Wiley, New York (1963)
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Mohamed Farook, N.A., Manochitra, S. & Afroos Banu, A. Kinetics and Mechanism of Oxidation of Substituted 4-Oxoacids by N-Bromosaccharin. J Solution Chem 42, 239–250 (2013). https://doi.org/10.1007/s10953-012-9942-0
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DOI: https://doi.org/10.1007/s10953-012-9942-0