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Enthalpy-entropy correlations in reactions of 2,4-dinitrophenyl benzoate with phenols in the presence of potassium hydrogen carbonate and with potassium phenoxides in dimethylformamide

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Abstract

Temperature dependences of the relative reactivity of substituted phenols RC6H4OH in the presence of potassium hydrogen carbonate and of potassium phenoxides RC6H4O−K+ toward 2,4-dinitrophenyl benzoate in dimethylformamide were studied using the competitive reactions technique. Correlation analysis of the relative rate constants k R/k H and differences in the activation parameters (ΔΔH ≠ and ΔΔS ≠) of competitive reactions revealed the existence of two isokinetic series for each type of nucleophiles. The mechanism of transesterification was interpreted in terms of an approach based on analysis of the effect of substituent in the nucleophile on the activation parameters.

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References

  1. Carey, F.A. and Sundberg, R.J., Advanced Organic Chemistry. Part A: Structure and Mechanisms, New York: Springer, 2007, 5th ed., chap. 3.

    Google Scholar 

  2. Adler, M., Adler, S., and Boche, G., J. Phys. Org. Chem., 2005, vol. 18, p. 193.

    Article  CAS  Google Scholar 

  3. Williams, A., Concerted Organic and Bio-organic Mechanisms, Boca Raton, FL: CRC, 2000.

    Google Scholar 

  4. Um, I.-H., Min, J.-S., Jeon, J.S., and Kwon, D.-S., Bull. Korean Chem. Soc., 1995, vol. 16, p. 569.

    CAS  Google Scholar 

  5. Kwon, D.-S., Park, J.-Y., and Um, I.-H., Bull. Korean Chem. Soc., 1994, vol. 15, p. 861.

    Google Scholar 

  6. Ba-Saif, S.A., Colthurst, M., Waring, M.A., and Williams, A., J. Chem. Soc., Perkin Trans. 2, 1991, p. 1901.

  7. Ba-Saif, S., Luthra, A.K., and Williams, A., J. Am. Chem. Soc., 1989, vol. 111, p. 2647.

    Article  CAS  Google Scholar 

  8. Os’kina, I.A. and Vlasov, V.M., Russ. J. Org. Chem., 2006, vol. 42, p. 865.

    Article  Google Scholar 

  9. Khalfina, I.A. and Vlasov, V.M., Russ. J. Org. Chem., 2008, vol. 44, p. 1619.

    Article  CAS  Google Scholar 

  10. Hansch, C., Leo, A., and Taft, R.W., Chem. Rev., 1991, vol. 91, p. 165.

    Article  CAS  Google Scholar 

  11. Bordwell, F.G. and Cheng, J.P., J. Am. Chem. Soc., 1991, vol. 113, p. 1736.

    Article  CAS  Google Scholar 

  12. Maran, F., Celadon, D., Severin, M.G., and Vianello, E., J. Am. Chem. Soc., 1991, vol. 113, p. 9320.

    Article  CAS  Google Scholar 

  13. Liu, L. and Guo, Q.X., Chem. Rev., 2001, vol. 101, p. 673; Linert, W. and Jameson, R.F., Chem. Soc. Rev., 1989, vol. 18, p. 477; Linert, W., Chem. Soc. Rev., 1994, vol. 23, p. 429; Exner, O., Chem. Commun., 2000, p. 1655.

    Article  CAS  Google Scholar 

  14. Ruff, F. and Farkas, Ö., J. Org. Chem., 2006, vol. 71, p. 3409; Ruff, F., Internet Electron. J. Mol. Des., 2004, vol. 3, p. 474; Ruff, F., J. Mol. Struct. (Theochem), 2003, vol. 625, p. 111; Ruff, F., J. Mol. Struct. (Theochem), 2002, vol. 617, p. 31.

    Article  CAS  Google Scholar 

  15. Leffler, J.E. and Grunwald, E., Rates and Equilibria of Organic Reactions as Treated by Statistical, Thermodynamic, and Extrathermodynamic Methods, New York: Wiley, 1963, chap. 9.

    Google Scholar 

  16. Um, I.-H., Park, Y.-M., Fujio, M., Mishima, M., and Tsuno, Y., J. Org. Chem., 2007, vol. 72, p. 4816; Oh, H.K., Oh, J.Y., Sung, D.D., and Lee, I., J. Org. Chem., 2005, vol. 70, p. 5624; Castro, E.A., Aguayo, R., Bessolo, J., and Santos, J.G., J. Org. Chem., 2005, vol. 70, p. 7788.

    Article  CAS  Google Scholar 

  17. Vlasov, V.M., New J. Chem., 2009, vol. 33, p. 501.

    Article  CAS  Google Scholar 

  18. Koh, H.J., Han, K.L., Lee, H.W., and Lee, I., J. Org. Chem., 1998, vol. 63, p. 9834.

    Article  CAS  Google Scholar 

  19. Koh, H.J., Kang, S.J., Kim, Ch. J., Lee, H.W., and Lee, I., Bull Korean Chem. Soc., 2003, vol. 24, p. 925.

    Article  CAS  Google Scholar 

  20. Oh, H.K., Kim, C.K., Lee, H.W., and Lee, I., J. Chem. Soc., Perkin Trans. 2, 2001, p. 1753.

  21. Alberghina, G., Arcoria, A., and Fisichella, S., J. Org. Chem., 1978, vol. 43, p. 1122.

    Article  CAS  Google Scholar 

  22. Arcoria, A. and Fisichella, S., J. Org. Chem., 1973, vol. 38, p. 3774.

    Article  CAS  Google Scholar 

  23. Yew, K.H., Koh, H.J., Lee, H.W., and Lee, I., J. Chem. Soc., Perkin Trans. 2, 1995, p. 2263.

  24. Exner, O., Progress in Physical Organic Chemistry, Streitwieser, A. and Taft, R.W., Eds., New York: Wiley, 1973, vol. 10, p. 411.

    Chapter  Google Scholar 

  25. Khalfina, I.A., Beregovaya, I.V., and Vlasov, V.M., Russ. J. Org. Chem., 2003, vol. 39, p. 1104.

    Article  CAS  Google Scholar 

  26. Correlation Analysis in Chemistry: Recent Advances, Chapman, N.B. and Shorter, J., Eds., New York: Plenum, 1978, p. 336.

    Google Scholar 

  27. Knyazev, V.N. and Drozd, V.N., Russ. J. Org. Chem., 1995, vol. 31, p. 1.

    Google Scholar 

  28. Oh, H.K., Kim, S.K., Lee, H.W., and Lee, I., New J. Chem., 2001, vol. 25, p. 313; Oh, H.K., Kim, S.K., Cho, I.H., Lee, H.W., and Lee, I., J. Chem. Soc., Perkin Trans. 2, 2000, p. 2306; Oh, H.K., Kim, S.K., Lee, H.W., and Lee, I., J. Chem. Soc., Perkin Trans. 2, 2000, p. 2306.

    Article  Google Scholar 

  29. Iogansen, I.V. and Rezenberg, M.Sh., Zh. Prikl. Spektrosk., 1968, vol. 9, p. 1027.

    CAS  Google Scholar 

  30. Kym, O., Ber., 1899, vol. 32, p. 1427.

    CAS  Google Scholar 

  31. Lee, C.K., Yu, J.S., and Lee, U.-J., J. Heterocycl. Chem., 2002, p. 1207; Wagner, G. and Horn, H., Pharmazie, 1973, vol. 28, p. 427.

  32. Williams, F.J. and Donahue, P.E., J. Org. Chem., 1977, vol. 42, p. 3414.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, pr. Akademika Lavrent’eva 9, Novosibirsk, 630090, Russia

    I. A. Khalfina & V. M. Vlasov

  2. Novosibirsk State University, Novosibirsk, Russia

    I. A. Khalfina

Authors
  1. I. A. Khalfina
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  2. V. M. Vlasov
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Correspondence to V. M. Vlasov.

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Original Russian Text © I.A. Khalfina, V.M. Vlasov, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 6, pp. 833–841.

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Khalfina, I.A., Vlasov, V.M. Enthalpy-entropy correlations in reactions of 2,4-dinitrophenyl benzoate with phenols in the presence of potassium hydrogen carbonate and with potassium phenoxides in dimethylformamide. Russ J Org Chem 47, 845–854 (2011). https://doi.org/10.1134/S1070428011060030

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  • DOI: https://doi.org/10.1134/S1070428011060030

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