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Role of added chloride ions in alteration of reaction pathway in the oxidation of cyclic ketones by dichloroisocyanuric acid—A kinetic study

  • Chemical Kinetics and Catalysis
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Abstract

Effect of added chloride ions on kinetics and pathway of reaction between cyclic ketones (five to eight membered rings) and dichloroisocyanuric acid (DCICA) was studied in aqueous acetic acid—perchloric acid medium. Formation of aliphatic dicarboxylic acids as the end products demonstrates the ring cleavage oxidation. Positive effect of acid and negative effect of dielectric constant on the reaction rate reveals a interaction between positive ion (oxidant in the form of H2OCl+) and dipolar substrate molecule. Zero and first orders by oxidant in absence and presence of added chloride ions illustrates the participation of substrate as enolic form of ketone and protonated ketone, respectively, in the rate determining steps. The observed order of reactivity of cyclic ketones (cyclohexanone > cyclooctanone > cyclopentanone > cycloheptanone) was explained on the bases of ring strain, change of hybridization and conformational considerations. The envisaged plausible mechanism based on order of reactants in presence and absence of added chloride ions was substantiated by the order of Arrhenius parameters.

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References

  1. A. R. Nadig, H. S. Yathirajan, and Rangaswamy, J. Ind. Chem. Soc. 66, 373 (1989).

    CAS  Google Scholar 

  2. M. K. Pillay and R. Kasthuri, Ind. J. Chem. B 37, 544 (1998).

    Google Scholar 

  3. P. Marigangaiah, Nath, and K. K. Banerji, Aust. J. Chem. 29, 1939 (1976).

    Article  CAS  Google Scholar 

  4. P. S. R. Murti and M. D. P. Rao, Ind. J. Chem. A 15, 524 (1977).

    Google Scholar 

  5. P. S. R. Murti and S. Devi, Ind. J. Chem. A 14, 399 (1976).

    Google Scholar 

  6. K. Vijayamohan, P. R. Rao, and E. V. Sundaram, J. Ind. Chem. Soc. 65, 91 (1988)

    Google Scholar 

  7. A. Podgorsek, S. Stavber, M. Zupana, and J. Iskra, Green Chem. 9, 1212 (2007).

    Article  CAS  Google Scholar 

  8. T. Nishiyama, O. N. O. Yasuhiro, S. Kurokawa, and S. Kimura, Chem. Pharm. Bull. 48, 1999 (2000).

    Article  CAS  Google Scholar 

  9. S. K. Mishra and Y. K. Gupta, J. Inorg. Nucl. Chem. 30, 2991 (1968).

    Article  CAS  Google Scholar 

  10. K. Balazs, I. Nagypal, G. Peintler, and A. K. Horvath, Inorg. Chem. 47, 7914 (2008).

    Article  Google Scholar 

  11. P. S. Radhakrishnamurti, N. K. Rath, and R. K. Panda, J. Chem. Soc. Perkin Trans. II 4, 517 (1987).

    Article  Google Scholar 

  12. P. S. Radhakrishnamurti and N. K. Rath, Ind. J. Chem. A 24, 300 (1985).

    Google Scholar 

  13. Y. Lakshman Kumar, R. Venkata Nadh, and P. S. Radhakrishnamurti, Bull. Chem. Soc. Ethiopia (in press).

  14. P. S. Radhakrishna Murti and S. Devi, Ind. J. Chem. A 14, 399 (1975).

    Google Scholar 

  15. K. Rajalakshmi, T. Ramachandramoorthy, and S. Srinivasan, J. Chem. Pharm. Res. 4, 894 (2012).

    CAS  Google Scholar 

  16. C. G. Swain, E. C. Stivers, J. F. Reuwer, Jr., and L. J. Schaad, J. Am. Chem. Soc. 80, 5885 (1958).

    Article  CAS  Google Scholar 

  17. S. Meenakshisundaram and R. Markkandan, J. Chem. Res. 2003, 679 (2003).

    Article  Google Scholar 

  18. R. T. Mahesh, M. B. Bellakki, and S. T. Nandibewoor, Catal. Lett. 97, 91 (2004).

    Article  CAS  Google Scholar 

  19. M. Gupta, K. Saha Swapan, and P. Banerjee, Int. J. Chem. Kinet. 22, 81 (1990).

    Article  CAS  Google Scholar 

  20. F. Feigl, Spot Test in Organic Analysis (Elsevier, Amsterdam, 1966), p. 325.

    Google Scholar 

  21. N. Madhavi, B. S. Sundar, and P. S. Radhakrishnamurti, Oxid. Commun. 29, 304 (2006).

    CAS  Google Scholar 

  22. L. N. Palo, PhD Thesis (Univ. Berhampur, India, 1990).

  23. R. R. Nagori, M. Mehta, and R. N. Mehrotra, J. Chem. Soc. Dalton Trans., 581 (1981).

    Google Scholar 

  24. J. Anil Kumar, and S. Sondu, Ind. J Chem. A 46, 1792 (2007).

    Google Scholar 

  25. S. Khan, M. U. Khan, S. Sanjay Kumar, H. D. Gupta, and P. K. Singh, Asian J. Chem. 15, 595 (2003).

    CAS  Google Scholar 

  26. V. S. Kiranmai Kolachana, C. Kishore, W. M. Kayani, G. K. Kouassi, R. V. Jagadeesh, and N. M. Made Gowda, Am. J. Org. Chem. 2, 18 (2012).

    Article  Google Scholar 

  27. V. Priya, M. Balasubramaniyan, and N. Mathiyalagan, J. Chem. Pharm. Res. 3, 522 (2011).

    CAS  Google Scholar 

  28. K. V. Sarkanen, Pure Appl. Chem. 5, 219 (1962).

    Article  CAS  Google Scholar 

  29. S. Parimala Vaijayanthi and N. Mathiyalagan, Int. J. Res. Pharm. Chem. 2, 722 (2012).

    CAS  Google Scholar 

  30. M. Deborde, and U. von Gunten, Water Res. 42, 13 (2008).

    Article  CAS  Google Scholar 

  31. S. Das, E. R. Rani, and M. K. Mahanti, Kinet. Catal. 48, 381 (2007)

    Article  CAS  Google Scholar 

  32. A. K. Sambasiva Rao, B. S. Sunder, and P. S. Radhakrishnamurti, Chem. Abstr. 144, 6390 (2006).

    Google Scholar 

  33. H. C. Brown, J. Org. Chem. 22, 439 (1957).

    Article  CAS  Google Scholar 

  34. D. Nasipuri, Stereochemistry of Organic Compounds (Wiley Eastern, New Delhi, 1994), p. 282.

    Google Scholar 

  35. J. Miewon, Bull. Korean Chem. Soc. 12, 224 (1991).

    Google Scholar 

  36. H. Shechter, M. J. Collins, R. Dessy, Y. Okuzum, and A. Cheuj, Am. Chem. Soc. 84, 2905 (1962).

    Article  Google Scholar 

  37. W. Nick Henry and S. Banerjee, Can. J. Chem. 55, 173 (1977).

    Article  Google Scholar 

  38. A. Gero, J. Am. Chem. Soc. 26, 3156 (1961).

    CAS  Google Scholar 

  39. A. Sabesan and N. V. Subramanian, Ind. J. Chem. 9, 942 (1971).

    CAS  Google Scholar 

  40. H. C. Brown and K. Ichikawa, Tetrahedron 1, 221 (1957).

    Article  CAS  Google Scholar 

  41. E. L. Eliel, Stereochemistry of Carbon Compounds (Tata McGraw-Hill, New Delhi, 1975).

    Google Scholar 

  42. C. K. Ingold, Structure and Mechanism in Organic Chemistry (Bell, London, 1953).

    Google Scholar 

  43. D. H. R. Barton, R. C. Cookson, W. Klyne, and C. W. Shoppee, Chem. Ind., 21 (1954).

    Google Scholar 

  44. F. A. L. Anet, M. St. Jacques, P. M. Henricks, A. K. Cheng, J. Krane, and L. Wong, Tetrahedron 30, 1629 (1974)

    Article  CAS  Google Scholar 

  45. A. N. Palaniappan, S. Vaideki, S. Srinivasan, and C. Raju, J. Chem. Pharm. Res. 4, 640 (2012)

    CAS  Google Scholar 

  46. F. A. L. Anet, Conformational Analysis: Scope and Present Limitation (Academic Press, 1971), p. 15.

    Book  Google Scholar 

  47. W. D. Chandler and L. Goodman, J. Mol. Spectrosc. 35, 232 (1970).

    Article  CAS  Google Scholar 

  48. F. V. Brutcher, T. Roberts, Jr., S. J. Barr, and S. Pearson, J. Am. Chem. Soc. 81, 4915 (1959).

    Article  CAS  Google Scholar 

  49. N. L. Allinger, J. Org. Chem. 10, 328 (1954).

    CAS  Google Scholar 

  50. K. S. Vasudevan and N. Venkatasubramanian, Ind. J. Chem. A 24, 304 (1985).

    Google Scholar 

  51. S. P. Mushran, K. Singh, L. Pandey, and S. M. Pandey, Proc. Ind. Natl. Sci. Acad. A 46, 119 (1980).

    CAS  Google Scholar 

  52. P. S. Radhakrishnamurti and D. K. Mahapatro, Ind. J. Chem. A 19, 207 (1980).

    Google Scholar 

  53. P. S. Radhakrishnamurti and D. K. Mahapatro, Ind. J. Chem. A 18, 53 (1979).

    Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, TJPS (PG) College, Guntur, 522006, India

    Y. Lakshman Kumar & P. S. Radhakrishnamurti

  2. School of Biotechnology, Vignan University, Vadlamudi, 522213, India

    R. Venkata Nadh

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  1. Y. Lakshman Kumar
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  2. R. Venkata Nadh
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  3. P. S. Radhakrishnamurti
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Correspondence to R. Venkata Nadh.

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Lakshman Kumar, Y., Venkata Nadh, R. & Radhakrishnamurti, P.S. Role of added chloride ions in alteration of reaction pathway in the oxidation of cyclic ketones by dichloroisocyanuric acid—A kinetic study. Russ. J. Phys. Chem. 89, 376–383 (2015). https://doi.org/10.1134/S0036024415030176

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