Skip to main content
Log in

Kinetics of Oxidation of 4-Oxoacids by N-Chlorosaccharin in Aqueous Acetic Acid Medium

  • Original Paper
  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

The oxidation kinetics of substituted and unsubstituted 4-oxoacids (S) by N-chlorosaccharin (NCSA) have been studied in aqueous acetic acid media. The reaction follows first-order kinetics in each of the 4-oxoacids, NCSA and H+. The effect of changes in the electronic nature of the substrate reveals that positive charge develops in the transition state. Based on the kinetic results and product analysis, a suitable mechanism has been proposed for the reaction of NCSA with 4-oxoacids.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. 1. Basheer Ahamed, K.-A., Sikkandar, G., Kannan, S.: Kinetics of oxidation of 4-oxoacids by permanganate in buffer media. Indian J. Chem. 38A, 183–186 (1999)

    Google Scholar 

  2. 2. (a) Sundaram, G.-S., Venkatasubramanian, N.: Oxidation of diphenylmethanol by bromamine T–A kinetic and mechanistic study. J. Chem. Soc. Perkin Trans. 2, 949–954 (1983); (b) Sharma, J.-P., Singh, R.-N.-P., Singh, A.-K., Singh, B.: Kinetics and mechanism of Ru(III) catalysed oxidation of some polyhydric alcohols by N-bromosuccinimide in acidic media. Tetrahedron 42, 2739–2747 (1986); (c) Ramachandrappa, R., Puttaswamy, M., Mayanna, S.-M., Made Gowda, N.-M.: Kinetics and mechanism of oxidation of aspirin by bromamine-T, N-bbromosuccinimide, and N-bromophthalimide. Int. J. Chem. Kinet. 30, 407–414 (1998); (d) Harihar, A.-L., Kembhavi, M.-R., Nandibewoor, S.-T.: Kinetics and mechanism of N-bromosuccinimide oxidation of L-arginine in aqueous acidic medium. J. Indian Chem. Soc. 76, 128–130 (1999); (e) Singh, A.-K., Rahmani, S., Singh, K.-V., Gupta, V., Kesarwani, D., Singh, B.: Iridium(III) catalysis of N-bromosuccinimide oxidation of reducing sugars in aqueous acid. Indian J. Chem. 40, 519–523 (2001)

    Google Scholar 

  3. 3. Negi, S.-C., Banerji, K.-K.: Kinetics and mechanism of the oxidation of secondary alcohols by N-bromoacetamide in acid medium. Indian J. Chem. 21B, 846–848 (1982)

    CAS  Google Scholar 

  4. 4. (a) Thimme Gowda, B., Ishwara Bhat, J.: Kinetics and mechanism of oxidation of thiosemicarbazidde by N-chloro- and N-bromo-seccinimides in aqueous and partially aqueous media. Indian J. Chem. 28A, 211–216 (1989); (b) Sukla, A., Upadhyay, S.-K.: Kinetics and mechanism of iridium(III) catalysed oxidation of aliphatic amines by N-bromosuccinimide. J. Indian Chem Soc. 11, 745–750 (1992); (c) Gopalakrishnan, G., John, L.-H.: Kinetic and mechanistic studies of the N-bromosuccinimide-promoted oxidative decarboxylation of glycine, DL-alanine, and DL-valine. J. Org. Chem. 50, 1206–1212 (1985); (d) Bharat, S., Lalji, P., Sharma, J., Pandey, S.: Mechanism of oxidation of some aliphatic ketones by N-bromosuccinimide in acidic media. Tetrahedron 38, 169–172 (1982)

    Google Scholar 

  5. 5. (a) 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); (b) Sikkandar, G.: Kinetics of oxidatative decarboxylation of β-benzoylpropionic acid by manganese(III) acetate. Asian J. Chem. 12, 1037–1040 (2000)

    Google Scholar 

  6. 6. Srinivasan, C., Rajagopal, S., Chellamani, A.: Mechanism of picolinic-acid-catalysed chromium(VI) oxidation of alkyl, aryl and diphenyl sulphides. J. Chem. Soc., Perkin Trans. 2, 1839–1844 (1990)

    Google Scholar 

  7. 7. Bishnoi, M.-L., Negi, S.-C., Banerji, K.-K.: Kinetics and mechanism of oxidation of some α-hydroxy acids by N-bromoacetamide in perchloric acid solution. Indian J. Chem. 25A, 660–662 (1986)

    CAS  Google Scholar 

  8. 8. (a) Khan, S., Khan, M.-U., Singh, S.-K., Gupta, H.-D., Singh, P.-K.: Kinetic and mechanistic investigation of N-chlorosaccharin oxidation of 2-alkanones. Asian J. Chem. 15, 595–600 (2003); (b) 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. E-J. Chem. 2, 127–131 (2004)

    CAS  Google Scholar 

  9. 9. 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)

    CAS  Google Scholar 

  10. 10. (a) 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); (b) 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. E-J. Chem. 2, 132–136 (2004); (c) Kavitha, S., Pandurangan, A., Alphones, I.: Kinetics and mechanism of oxidation of betabenzoylpropionic acids by pyridinium fluorochromate in aqueous acetic acid medium. Indian J. Chem. 44A, 715–718 (2005)

    Google Scholar 

  11. 11. 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 (1986)

    CAS  Google Scholar 

  12. 12. 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)

    Article  Google Scholar 

  13. 13. (a) Wiberg, K.-B.:Physical Organic Chemistry. John Wiley, New York pp. 416–420, (1964); (b) Gould E.-S.: Mechanism and structure in Organic Chemistry. Holt Reinhart and Winston, New York, pp. 181–185 (1964)

    Google Scholar 

  14. 14. (a) Richard Johnes, A.-Y.: Physical and Mechanistic Organic Chemistry. Cambridge Univ. Press, New York p. 42 (1984) (b) Ruff, F., Kucsman, A.: Mechanism of the oxidation of sulphides with sodium periodate. J. Chem. Soc. Perkin Trans. 2, 683–688 (1985)

    Google Scholar 

  15. 15. Cotton, F.-A., Wilkinson, G.: Advanced Inorganic Chemistry. New York, 5th edn. John Wiley, p. 707 (1988)

  16. 16. Greenwood, N.-N., Earnshaw, A.: Chemistry of the Elements. Pergamon Press, Oxford p. 1222 (1984)

    Google Scholar 

  17. 17. Neil Issacs, S.: Physical Organic Chemistry. Longman Scientific & Technical, New York (1987)

    Google Scholar 

  18. 18. Leffler, J. -F., Grunwald, E.: Rates and Equilibrium of Organic Reactions. Wiley, New York (1963)

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to N. A. Mohamed Farook.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Farook, N.A.M. Kinetics of Oxidation of 4-Oxoacids by N-Chlorosaccharin in Aqueous Acetic Acid Medium. J Solution Chem 36, 345–356 (2007). https://doi.org/10.1007/s10953-006-9116-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-006-9116-z

Keywords

Navigation