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Investigations on Substituent and Solvent Effects of Solvolysis Reactions. VIII. The Influence of Water and Nonaqueous Solvents on the Imidazolysis of 4-Nitrophenyl Acetate

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Abstract

The aminolysis reaction of 4-nitrophenyl acetate with imidazole was investigated in water, acetonitrile, propylene carbonate, and 1,4-dioxane at different temperatures. the observed rates can be evaluated with the help of a reaction mechanism consisting of two competitive reaction paths; the first is the bimolecular nucleophilic substitution of the phenol moiety by imidazole; the second path is performed via general base catalysis by a second imidazole molecule. The rate constants of the bimolecular reaction are quantitatively correlated with the four-parameter Taft–Kamlet equation for solvent effects on chemical reactions. A qualitative interpretation of the data shows that the two reaction paths are influenced to the same extent by the solvent.

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REFERENCES

  1. J. Barthel, G. Bäder, and G. Schmeer, Z. Phys. Chem. [N.F.] 62, 63 (1964).

    Google Scholar 

  2. J. Barthel and G. Schmeer, Z. Phys. Chem. [N.F.] 71, 102 (1970).

    Google Scholar 

  3. G. Schmeer and J. Barthel, Z. Phys. Chem. [N.F.] 140, 17 (1984).

    Google Scholar 

  4. G. Schmeer, S. Riembauer, and J. Barthel, Z. Phys. Chem. [N.F.] 165, 45 (1989).

    Google Scholar 

  5. G. Schmeer, S. Riembauer, and J. Barthel, J. Solution Chem. 19, 1175 (1990).

    Google Scholar 

  6. F. M. Menger, J. Am. Chem. Soc. 88, 3081 (1966).

    Google Scholar 

  7. N. Nakamizo, Bull. Chem. Soc. Jpn. 42, 1071 (1969).

    Google Scholar 

  8. H. Anderson, C. W. Su, and J. W. Watson, J. Am. Chem. Soc. 91, 482 (1969).

    Google Scholar 

  9. D. P. N. Satchell and I. I. Secemski, J. Chem. Soc. B, p. 130 (1969).

  10. A. S. A. S. Shaeali and S. S. Biechler, J. Am. Chem. Soc. 89, 3020 (1967).

    Google Scholar 

  11. D. P. N. Satchell and I. I. Secemski, J. Chem. Soc. B, p. 1013 (1970).

  12. F. M. Menger and J. H. Smith, J. Am. Chem. Soc. 91, 5346 (1969).

    Google Scholar 

  13. M. L. Bender, Chem. Rev. 60, 53 (1960).

    Google Scholar 

  14. N. Gravitz and W. P. Jencks, J. Am. Chem. Soc. 96, 499 (1974).

    Google Scholar 

  15. M. J. Gresser and W. P. Jencks, J. Am. Chem. Soc. 99, 6963 (1977).

    Google Scholar 

  16. E. A. Castro and F. J. Gil, J. Am. Chem. Soc. 99, 7611 (1977).

    Google Scholar 

  17. W. P. Jencks, Catalysis in Chemistry and Enzymology (McGraw-Hill, New York, 1969).

    Google Scholar 

  18. H. Neuvonen, J. Chem. Soc., Perkin Trans. II, p. 159 (1987).

  19. T. C. Bruice and S. Benkovic, Bioorganic Mechanisms (Benjamin, New York, 1966), p. 22.

    Google Scholar 

  20. T. C. Bruice and G. L. Schmir, J. Am. Chem. Soc. 80, 148 (1958).

    Google Scholar 

  21. E. K. Euranto, Ann. Acad. Sci. Fenn. AII 152(3), 1 (1970).

    Google Scholar 

  22. F. M. Menger and J. H. Smith, J. Am. Chem. Soc. 94, 3824 (1972).

    Google Scholar 

  23. F. M. Menger and A. C. Vitale, J. Am. Chem. Soc. 95, 4931 (1973).

    Google Scholar 

  24. T. C. Bruice and S. J. Benkovic, J. Am. Chem. Soc. 86, 418 (1964).

    Google Scholar 

  25. M. L. Bender and B. W. Turnquest, J. Am. Chem. Soc. 79, 1652 (1957).

    Google Scholar 

  26. T. C. Bruice and G. L. Schmir, J. Am. Chem. Soc. 79, 1663 (1957).

    Google Scholar 

  27. W. P. Jencks and M. Gilchrist, J. Am. Chem. Soc. 90, 2622 (1968).

    Google Scholar 

  28. J. F. Kirsch and W. P. Jencks, J. Am. Chem. Soc. 86, 833 (1964).

    Google Scholar 

  29. J. F. Kirsch and W. P. Jencks, J. Am. Chem. soc. 86, 837 (1964).

    Google Scholar 

  30. J. P. Lee, R. Bembi, and T. H. Fife, J. Org. Chem. 62, 2872 (1997).

    Google Scholar 

  31. T. H. Fife, Acc. Chem. Res. 26, 325 (1993).

    Google Scholar 

  32. K. Pralat and G. Czechowski, J. Mol. Liquids 38, 147 (1988).

    Google Scholar 

  33. J. L. Hogg, R. Morris III, and N. A. Durrant, J. Am. Chem. Soc. 100, 1590 (1978).

    Google Scholar 

  34. D. M. Blow, J. J. Birktoft, and B. S. Hartley, Nature 221, 337 (1969).

    Google Scholar 

  35. Y. I. Khurgin and T. N. Filatova, Bull. Acad. Sci. USSR Div. Chem. Ser. 22, 1157 (1973).

    Google Scholar 

  36. Y. I. Khurgin and T. N. Filatova, Bull. Acad. Sci. USSR Div. Chem. Ser. 22, 2255 (1973).

    Google Scholar 

  37. G. Wallerberg, J. Boger, and P. Haake, J. Am. Chem. Soc. 93, 4938 (1971).

    Google Scholar 

  38. Y. Pocker and D. L. Ellsworth, J. Am. Chem. Soc. 99, 2284 (1977).

    Google Scholar 

  39. M. J. Kamlet, J. L. M. Abboud, M. H. Abraham, and R. W. Taft, J. Org. Chem. 48, 2877 (1983).

    Google Scholar 

  40. Y. Marcus, Ion Solvation (Wiley, New York, 1985).

    Google Scholar 

  41. J. Barthel and H. J. Gores, in Solution Chemistry: A Cutting Edge in Modern Technology, G. Mamantov and A. I. Popov, eds. (VCH, New York, 1994), Chap. 1.

    Google Scholar 

  42. F. Takahashi, Nippon Kagaku Zasshi 91, 617 (1970).

    Google Scholar 

  43. H. Neuvonen, J. Chem. Soc. Perkin Trans. II, p. 669 (1990).

  44. J. G. Kirkwood, J. Chem. Phys. 2, 351 (1934).

    Google Scholar 

  45. K. J. Laidler and P. A. Landskroener, J. Chem. Soc. Faraday Trans. 52, 200 (1956).

    Google Scholar 

  46. M. J. Kamlet, J. L. M. Abboud, and R. W. Taft, J. Am. Chem. Soc. 99, 6027 (1977).

    Google Scholar 

  47. C. Reichardt, in Solvent and Solvent Effects in Organic Chemistry (Verlag Chemie, Weinheim, 1988).

    Google Scholar 

  48. M. J. Kamlet and R. W. Taft, J. Am. Chem. Soc. 98, 377 (1976).

    Google Scholar 

  49. M. J. Kamlet and R. W. Taft, J. Am. Chem. Soc. 98, 2886 (1976).

    Google Scholar 

  50. G. E. P. Box, W. G. Hunter, and J. S. Hunter, Statistics for Experimenters, An Introduction to Design, Data Analysis, and Model Building (Wiley, New York, 1978).

    Google Scholar 

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Author notes

  1. C. Six

    Present address: Bayer AG, PU-F/VF, D-41538, Dormagen, Germany

Authors and Affiliations

  1. Institute of Physical and Theoretical Chemistry, University of Regensburg, D-93040, Regensburg, Germany

    G. Schmeer & C. Six

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  1. G. Schmeer
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  2. C. Six
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  3. J. Steinkirchner
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Schmeer, G., Six, C. & Steinkirchner, J. Investigations on Substituent and Solvent Effects of Solvolysis Reactions. VIII. The Influence of Water and Nonaqueous Solvents on the Imidazolysis of 4-Nitrophenyl Acetate. Journal of Solution Chemistry 28, 211–222 (1999). https://doi.org/10.1023/A:1021706331026

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