Abstract
The kinetics of oxidation of a series of substituted 4-oxobutanoic acids (Y–C6H4COCH2CH2COOH: Y = H, OCH3, CH3, C6H5, Cl, Br or NO2) by N-bromophthalimide have been studied in aqueous acetic acid medium at 30 °C. The total reaction is second-order, first-order each in oxidant and substrate. The oxidation rate increases linearly with [H+], establishing the hypobromous acidium ion, H2O+Br, as the reactive species. A variation in 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 on the electronic nature of the substrate reveals that there is a development of positive charge in the transition state. The activation parameters have been computed from Arrhenius and Eyring plots. Based on the kinetic results, a suitable mechanism has been proposed.
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References
Sanjeeva Reddy, C., Sunitha Manjari, P.: Kinetics and mechanism of acid bromate oxidation of substituted 4-oxoacids. Indian J. Chem 49A, 418–424 (2010)
Kolvari, E., Ghorbani-Choghamarani, A., Salehi, P., Shirini, F., Zolfigal, M.A.: Applications of N-halo reagents in organic synthesis. J. Iran. Chem. Soc. 4, 126–171 (2007)
Armesto, X.L., Canie, L.M., Garcia, M.V., Santaballa, J.A.: Aqueous chemistry of N-halo compounds. Chem. Soc. Rev. 27, 453–460 (1998)
Meenakshisundaram, S., Markandan, R.: Os(VIII)-catalysis on the oxidation of some diaryl sulphoxides with bromamine-B in alkaline medium. Indian J. Chem. 44A, 71–75 (2005)
Meenakshisundaram, S., Selvaraju, M.: Kinetics and mechanism of the reaction of α-phenoxypropionic acids with sodium salt of N-chlorobenzenesulphonamide: EDTA catalysis. Int. J. Chem. Kinet. 34, 27–33 (2002)
Gurumurthy, R., Sathyanarayanan, K.I., Gopalakrishnan, M.: Kinetics and mechanism of oxidation of ethyl phenylthioacetates by bromamine-B. Bull. Chem. Soc. Jpn. 65, 1096–1100 (1992)
Ananda Murthy, A.S., Ananda Murthy, S., Mahadevappa, D.S.: Oxidation of thiols by sodium N-haloarylsulphonamides. Talanta 36, 1051–1054 (1989)
Mahadevapp, D.S., Mohan, K., Ananda, S.: Oxidation of aliphatic ketones by bromamine-B: a kinetic study. Tetrahedron 42, 4857–4866 (1986)
Mukherjee, J., Banerji, K.K.: Kinetics and mechanism of the oxidation of substituted benzyl alcohols by sodium N-chlorobenzenesulphonamide. J. Chem. Soc. Perkin Trans. 2, 676–678 (1980)
Mohamed Farook, N.A., Seyed Dameem, G.A.: Kinetics of oxidation of 3-benzoylpropionic acid by N-chlorobenzamide in aqueous acetic acid medium. E-J Chem. 8, 561–564 (2011)
Saxena, M., Gupta, R., Singh, A., Singh, B., Singh, A.K.: Kinetics and mechanism of oxidation of some hydroxyl acids by N-bromoacetamide. J. Mol. Catal. 65, 317–327 (1991)
Bishnoi, M.L., Negi, S.C., Banerji, K.K.: Kinetics & mechanism of oxidation of some α-hydroxy acids by N-bromoacetamide in perchloric acid solution. Indian J. Chem. 25A, 660–662 (1986)
Komal Reddy, M., Sanjeeva Reddy, C.H., Sundaram, E.V.: Oxidative kinetics of aminoacids by N-bromoacetamide—a study of solvent effect and general base catalysis. Tetrahedron 41, 3071–3081 (1985)
Kissane, M., Murphy, M., Lynch, D., Ford, A., Maguire, A.R.: Investigation of the reaction of α-thioamides, α-esters and α-nitriles with N-halosuccinimides. Tetrahedron 64, 7639–7649 (2008)
Mohamed Farook, N.A.: Kinetics of oxidation of 4-oxo acids by N-bromosuccinimide in aqueous acetic acid medium. J. Iran. Chem. Soc. 3, 378–386 (2006)
Mathiyalagan, N., Sridharan, R.: Kinetics and mechanism of oxidation of aromatic aldehydes by N-chlorosuccinimide in aqueous acetic acid. Indian J. Chem. 44A, 2044–2047 (2005)
Thenraja, D., Subramaniam, P., Srinivasan, C.: Kinetics and mechanism of oxidation of aromatic sulphides and arylmercaptoacetic acids by N-chlorosuccinimide. J. Chem. Soc. Perkin Trans. 2, 2125–2129 (2002)
Waqar, C., Singh, B., Sharma, J.P.: Mechanism of Ru(III)-catalysed oxidation of glycollic and mandelic acids with N-bromosuccinimide in acidic media. J. Mol. Catal. 60, 49–58 (1990)
Vankar, Y.D., Kumaravel, G.: N-chlorosuccinimide/sodium iodide: a convenient source of N-iodosuccinimide. Synthesis of α-iodo carbonyl compounds and trans-1,2-iodoacetates. Tetrahedron Lett. 25, 233–236 (1984)
Cheung, Y.-F.: N-bromosuccinimide: direct oxidation of aldehydes to acid bromides. Tetrahedron Lett. 40, 3809–3810 (1979)
Srinivasan, N.S., Venkatasubramanian, N.: Oxidation of alcohols by N-chlorosuccinimde—a kinetic study. Tetrahedraon 30, 419–425 (1974)
Harville, R., Reed Jr, S.F.: Sulphide oxidation with N-halosuccinimides. J. Org. Chem. 10, 3976–3977 (1968)
Vivekanandam, K., Nambi, K.: N-chloronicotinamide: a new, mild, stable, efficient and inexpensive oxidant for organic substrates. Indian J. Chem. 35B, 1117–1118 (1996)
Kaur, R.D., Arora, N., Gujral, H., Kaur, G., Nayak, S.N., Singh, S.K.: Mineitc and mechanistic approach of N-chlorosaccharin oxidation of some non-vicinal poly hydroxyl alocohols. Int. J. ChemTech Res. 2, 1480–1485 (2010)
Mohamed Farook, N.A.: Kinetics of oxidation of 4-oxoacids by N-chlorosaccharin in aqueous acetic acid medium. Asian J. Chem. 19, 3727–3738 (2007)
Anjum, A., Srinivas, P.: Analytical and kinetic behavior of N-bromoimide–mercuric acetate system towards aromatic aldehydes: a mechanistic study. Asian J. Chem. 18, 673–678 (2006)
Mohana Das, C., Indrasenan, P.: N-Bromosaccharin as an oxidimetric titrant: direct potentiometric & visual titrations of some typical reductants in aqueous acetic acid medium. Indian J. Chem. 26A, 55–58 (1987)
Anjum, A., Srinivas, P.: Kinetics and mechanistic aspects of oxidation of acetophenones by N-bromophthalimide in presence of mercuric acetate. Asian J. Chem. 17, 553–558 (2005)
Thiagarajan, V., Shoba, Ramakrishnan: Oxidation of α-hydroxyacids by N-bromophthalimide—dependence of mechanism on pH of the medium. Indian J. Chem. 37B, 443–447 (1998)
De Barnet Barry, E., Sanders, F.G.: The synthesis of some homologous naphthalenes. J. Chem. Soc. (1933). doi:10.1039/JR9330000434
Vogel, A.I.: A Textbook of Practical Organic Chemistry, p. 737. Longmans Green, London (1962)
Hey, D.H., Wilkinson, R.: The preparation of 2-phenylnapthalen from diphenyl. J. Chem. Soc. (1940). doi:10.1039/JR9400001030
Srinivasan, C., Rajagopal, S., Chellamani, A.: J. Chem. Soc. Perkin Trans. 2, 1839–1844 (1990)
Vivekanandan, K., Nambi, K.: Kinetics and mechanism of oxidation of aminoacids by N-chloronicotinimide in aqueous acetic acid medium. J. Indian Chem. Soc. 76, 198–201 (1999)
Amis, E.S.: Solvent effects on reaction rates and mechanisms. Academic Press, New York (1967)
Bishnoi, M.L., Banerji, K.K.: Kinetics and mechanism of the oxidation of α-aminoacids by N-bromoacetamide. Tetrahedron 41, 6047–6050 (1985)
Uma, K.V., Mayanna, S.M.: Kinetics of oxidation of benzyl alcohols by sodium N-chloro-p-toluenesulphonamide. Int. J. Chem. Kinet. 12, 861–870 (1980)
Timme Gowda, B., Mahadevappa, D.S.: Chloraminometric reactions: kinetics and mechanisms of oxidations of aminoacids by sodium N-chloro-p-toluenesulphonamide in acid and alkaline media. J. Chem. Soc. Perkin Trans. 2, 323–334 (1983)
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, 722–726 (1986)
Nath, M.P., Banerji, K.K.: Kinetics and mechanism of the oxidation of methyl aryl ketones by acid permanganate. Aust. J. Chem. 29, 1939–1945 (1976)
Shorter, J.: The kinetics of oxidation of acetone by ceric ammonium nitrate in aqueous nitric acid. J. Chem. Soc. 1868–1876 (1962). doi:10.1039/JR9620001868
Wiberg, K.B., Schaefer, H.: Chromic acid oxidation of isopropylalcohol—the oxidation steps. J. Am. Chem. Soc. 91, 933–937 (1969)
Nathan, W.S., Waston, H.B.: Constitutional factors controlling prototropic changes in carbonyl compounds. Part III. The prototropy of nuclear-substituted acetophenones. J. Chem. Soc. 217–220 (1933). doi:10.1039/JR9330000217
Cotton, F.A., Wilkinson, G.: Advanced Inorganic Chemistry, 5th edn, p. 707. Wiley, New York (1988)
Greenwood, N.N., Earnshaw, A.: Chemistry of the Elements, p. 1222. Pergamon Press, Oxford (1984)
Leffler, J.F., Grunwald, E.: Rates and Equilibrium of Organic Reactions. Wiley, New York (1963)
Ritchie, C.D., Sager, W.F.: An examination of structure-reactivity relationships. Prog. Phys. Org. Chem. 2, 323–400 (1964)
Exner, O.: Determination of the isokinetic temperature. Nature 227, 366–367 (1970)
Exner, O.: Concerning the isokinetic relationship. Nature 201, 488–490 (1964)
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Mohamed Farook, N.A., Alhaji, N.M.I., Uduman Mohideen, A.M. et al. Kinetics and Mechanism of the Oxidation of 4-Oxo-4-arylbutanoic Acids by N-bromophthalimide in Aqueous Acetic Acid Medium. J Solution Chem 42, 1183–1193 (2013). https://doi.org/10.1007/s10953-013-0025-7
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DOI: https://doi.org/10.1007/s10953-013-0025-7