Skip to main content
SpringerLink
Log in

Kinetics and mechanism of monomolecular heterolysis of commercial organohalogen compounds: XLIII. Solvent effect on activation parameters of dehydrochlorination of 3-chloro-3-methylbut-1-ene. Correlation analysis of solvation effects

  • Published:
Russian Journal of General Chemistry Aims and scope Submit manuscript

Abstract

The influence of temperature on the rate of dehydrochlorination of 3-chloro-3-methylbut-1-ene in 17 aprotic and 13 protic solvents, ν = k[C5H9Cl], was studied by the verdazyl method. In aprotic solvents, the electrophilicity, ionizing power, and cohesion of solvents decrease ΔG ≠ by increasing ΔS ≠. The nucleophilicity and polarizability increase both ΔH ≠ and ΔS ≠ to equal extent and therefore do not affect ΔG ≠. In protic solvents, the solvent nucleophilicity increases ΔH ≠ to a greater extent than ΔS ≠, and the overall effect of the nucleophilic solvation is small and negative.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Ponomarev, N.E., Zaliznyi, V.V., and Dvorko, G.F., Zh. Obshch. Khim., 2005, vol. 75, no. 10, p. 1593.

    Google Scholar 

  2. Ponomarev, N.E., Zaliznyi, V.V., and Dvorko, G.F., Zh. Obshch. Khim., 2005, vol. 75, no. 9, p. 1503.

    Google Scholar 

  3. Sneen, R.A., Carter, J.V., and Kay, P.S., J. Am. Chem. Soc., 1966, vol. 88, no. 11, p. 2594.

    Article  CAS  Google Scholar 

  4. Dvorko, G.F., Ponomarev, N.E., and Ponomareva, E.A., Zh. Obshch. Khim., 1999, vol. 69, no. 11, p. 1835.

    Google Scholar 

  5. Dvorko, G.F., Ponomareva, E.A., and Ponomarev, M.E., J. Phys. Org. Chem., 2004, vol. 17, no. 4, p. 825.

    Article  CAS  Google Scholar 

  6. Reichardt, Ch., Solvents and Solvent Effects in Organic Chemistry, Weinheim: VCH, 1988.

    Google Scholar 

  7. Dvorko, G.F., Pervishko, T.L., Golovko, N.I., Vasil’kevich, A.I., and Ponomareva, E.A., Zh. Org. Khim., 1993, vol. 29, no. 9, p. 1805.

    Google Scholar 

  8. Ponomarev, N.E., Stambirskii, M.V., and Dvorko, G.F., Zh. Org. Khim., 2004, vol. 40, no. 4, p. 520.

    Google Scholar 

  9. Vasil’kevich, A.I., Ponomareva, E.A., and Dvorko, G.F., Zh. Org. Khim., 1990, vol. 26, no. 11, p. 2267.

    CAS  Google Scholar 

  10. Dvorko, G.F., Zaliznyi, V.V., and Ponomarev, N.E., Zh. Obshch. Khim., 2002, vol. 72, no. 10, p. 1644.

    Google Scholar 

  11. Isaacs, N.S., Physical Organic Chemistry, New York: Wiley, 1992.

    Google Scholar 

  12. Buncel, E., Millington, J.P., and Wiltshire, J.F., Can. J. Chem., 1977, vol. 55, no. 11, p. 1401.

    Article  CAS  Google Scholar 

  13. Quameneur, F., Baiou, B., and Kerfanto, M., C. R. Acad. Sci. Paris, 1974, vol. 278, no. 1, p. 299.

    Google Scholar 

  14. Abraham, M.H., Grellier, P.L., Nasehzadeh, A., and Walker, A.C., J. Chem. Soc., Perkin Trans. 2, 1988, no. 6, p. 1717.

  15. Dvorko, G.F., Zaliznyi, V.V., and Ponomarev, N.E., Zh. Obshch. Khim., 2002, vol. 72, no. 9, p. 1501.

    Google Scholar 

  16. Dvorko, G.F., Zaliznyi, V.V., and Ponomarev, N.E., Zh. Obshch. Khim., 2004, vol. 74, no. 9, p. 1470.

    Google Scholar 

  17. Dvorko, G.F. and Ponomareva, E.A., Usp. Khim., 1991, vol. 60, no. 10, p. 2089.

    CAS  Google Scholar 

  18. Amelichev, V.A., Trunov, Yu.P., and Saidov, G.V., Vestn. Leningr. Gos. Univ., Ser. 2: Khim., 1974, no. 10, p. 83.

  19. Dvorko, G.F. and Evtushenko, N.Yu., Zh. Obshch. Khim., 1991, vol. 61, no. 9, p. 205.

    Google Scholar 

  20. Koppel, I.A. and Palm, V.A., Advances in Linear Free Energy Relationship, Chapman, N.B. and Schoter, J., Eds., London: Plenum, 1972, p. 208.

    Google Scholar 

  21. Makitra, R.G. and Pirig, Ya.N., Zh. Obshch. Khim., 1986, vol. 56, no. 3, p. 657.

    CAS  Google Scholar 

  22. Kamlet, M.J. and Taft, R.W., J. Am. Chem. Soc., 1976, vol. 98, no. 2, p. 377.

    Article  CAS  Google Scholar 

  23. Marcus, Y., Chem. Soc. Rev., 1993, vol. 22, no. 3, p. 406.

    Google Scholar 

  24. Palm, V.A., Osnovy kolichestvennoi teorii organicheskikh reaktsii (Principles of the Quantitative Theory of Organic Reactions), Leningrad: Khimiya, 1977.

    Google Scholar 

  25. Abboud, J.-L. and Notario, R., Pure Appl. Chem., 1999, vol. 71, no. 4, p. 645.

    CAS  Google Scholar 

  26. Kafarov, V.V., Metody kibernetiki v khimii i khimicheskoi tekhnologii (Cybernetic Methods in Chemistry and Chemical Technology), Moscow: Khimiya, 1971.

    Google Scholar 

  27. Gajewski, J.J., J. Am. Chem. Soc., 2001, vol. 123, no. 44, p. 10 877.

    Article  CAS  Google Scholar 

  28. Dvorko, G.F., Koshchii, I.V., Prokopets, A.M., and Ponomareva, E.A., Zh. Obshch. Khim., 2002, vol. 72, no. 12, p. 1982.

    Google Scholar 

  29. McLennan, D.J. and Martin, P.L., J. Chem. Soc., Perkin Trans. 2, 1982, no. 6, p. 1091.

  30. Okuno, Y., J. Phys. Chem., 1999, vol. 103, no. 11, p. 190.

    CAS  Google Scholar 

  31. Yamabe, S. and Tsuchida, N., J. Comput. Chem., 2004, vol. 25, no. 4, p. 598.

    Article  CAS  Google Scholar 

  32. Okuno, Y., J. Am. Chem. Soc., 2000, vol. 122, no. 12, p. 2925.

    Article  CAS  Google Scholar 

  33. Hollenstein, S. and Laube, T., J. Am. Chem. Soc., 1993, vol. 115, no. 22, p. 7240.

    Article  CAS  Google Scholar 

  34. Jagannadham, V., Proc. Indian Acad. Sci., 2003, vol. 115, no. 1, p. 41.

    Article  CAS  Google Scholar 

  35. Dvorko, G.F., Vasil’kevich, A.I., and Ponomarev, N.E., Zh. Org. Khim., 1997, vol. 33, no. 2, p. 245.

    Google Scholar 

  36. Dvorko, G.F., Cherevach, T.V., Kulik, N.I., and Ponomarev, N.E., Zh. Obshch. Khim., 1994, vol. 64, no. 6, p. 979.

    CAS  Google Scholar 

  37. Dvorko, G.F., Koshchii, I.V., Prokopets, A.M., and Ponomareva, E.A., Zh. Obshch. Khim., 2002, vol. 72, no. 12, p. 1989.

    Google Scholar 

  38. Koshchii, I.V., Cand. Sci. (Chem.) Dissertation, Kiev, 2002.

  39. Ingold, C.K., Structure and Mechanism in Organic Chemistry, Ithaca: Cornell Univ. Press, 1969.

    Google Scholar 

  40. Okamoto, K., Nioto, I., Dohi, M., and Shingu, H., Bull. Chem. Soc. Jpn., 1971, vol. 44, no. 2, p. 320.

    Google Scholar 

  41. Kinoshita, T., Ueno, T., Ikai, K., Fujiwara, M., and Okamoto, K., Bull. Chem. Soc. Jpn., 1988, vol. 61, no. 12, p. 3273.

    Article  CAS  Google Scholar 

  42. Entelis, S.G. and Tiger, R.P., Kinetika reaktsii v zhidkoi faze (Kinetics of Liquid-Phase Reactions), Moscow: Khimiya, 1973.

    Google Scholar 

  43. Gorodynskii, V.A. and Morachevskii, A.A., Dokl. Akad. Nauk SSSR, 1975, vol. 224, no. 4, p. 855.

    Google Scholar 

  44. Kim, H.J. and Hynes, J.T., J. Am. Chem. Soc., 1992, vol. 114, no. 26, p. 10 508.

    CAS  Google Scholar 

  45. Jencks, W.P., Chem. Soc. Rev., 1980, vol. 10, no. 2, p. 345.

    Google Scholar 

  46. Claesson, S., Lundgren, B., and Szwarc, M., Trans. Faraday Soc., 1970, vol. 66, no. 9, p. 3053.

    Article  CAS  Google Scholar 

  47. Ponomareva, E.A., Pervischko, T.L., and Dvorko, G.F., Org. React. (Tartu), 1981, vol. 18, no. 2, p. 312.

    CAS  Google Scholar 

  48. Farcasin, D., Jähme, J., and Rüchardt, Ch., J. Am. Chem. Soc., 1985, vol. 107, no. 20, p. 5717.

    Article  Google Scholar 

  49. Zillian, U., Chem. Ztg., 1984, vol. 108, no. 2, p. 381.

    Google Scholar 

  50. Katriski, A.P. and Brycki, B., J. Am. Chem. Soc., 1986, vol. 108, no. 23, p. 7295.

    Article  Google Scholar 

  51. Winstein, S., Appel, B., Baker, K., and Diaz, L., J. Chem. Soc., Spec. Publ., 1965, no. 19, p. 109.

  52. Dvorko, G.F. and Ponomareva, E.A., Zh. Org. Khim., 1998, vol. 34, no. 4, p. 487.

    Google Scholar 

  53. Dvorko, G.F. and Ponomarev, N.E., Zh. Obshch. Khim., 1997, vol. 67, no. 6, p. 908.

    Google Scholar 

  54. Kelly, X.H., Tanaka, S.E., and Bennet, A.J., J. Am. Chem. Soc., 1998, vol. 120, no. 7, p. 1405.

    Article  Google Scholar 

  55. Mayr, H. and Minegishi, Sh., Angew. Chem., Int. Ed., 2002, vol. 41, no. 23, p. 4493.

    Article  CAS  Google Scholar 

  56. Richard, J.P., Toteva, M., and Amyes, T.L., Org. Lett., 2001, vol. 3, no. 14, p. 2225.

    Article  CAS  Google Scholar 

  57. Liu, K-I., J. Chin. Chem. Soc., 1995, vol. 42, no. 4, p. 607.

    CAS  Google Scholar 

  58. Takeuchi, K., Pure Appl. Chem., 1998, vol. 70, no. 10, p. 2023.

    CAS  Google Scholar 

  59. Bentley, T.W. and Llewellyn, G., Prog. Phys. Org. Chem., 1990, vol. 17, p. 121.

    Article  CAS  Google Scholar 

  60. Kevill, D.N. and D’souza, M.J., J. Phys. Org. Chem., 1992, vol. 5, no. 3, p. 287.

    Article  CAS  Google Scholar 

  61. Takeuchi, K., Takasuka, M., Shiba, E., Kinoshita, T., Okazaki, T., Abboud, J.-L., Notario, R., and Castano, O., J. Am. Chem. Soc., 2000, vol. 122, no. 30, p. 7351.

    Article  CAS  Google Scholar 

  62. Dvorko, G.F., Koshchii, I.V., and Ponomareva, E.A., Zh. Obshch. Khim., 2003, vol. 73, no. 4, p. 603.

    Google Scholar 

  63. Dvorko, G.F., Koshchii, I.V., and Ponomareva, E.A., Zh. Obshch. Khim., 2003, vol. 73, no. 3, p. 404.

    Google Scholar 

  64. Dvorko, G.F. and Ponomar’ova, E.O., Ukr. Khim. Zh., 1993, vol. 59, no. 11, p. 1190.

    CAS  Google Scholar 

  65. Abboud, J.-L., Herreros, M., Notario, R., Lomas, J.S., Madera, J., Mullea, P., and Rossier, J.-C., J. Org. Chem., 1999, vol. 64, no. 16, p. 6401.

    Article  CAS  Google Scholar 

  66. Abboud, J-L.M., Castano, O., Della, E.W., Herreros, M., Muller, P., Notario, R., and Rossier, J-C., J. Am. Chem. Soc., 1997, vol. 119, no. 9, p. 2262.

    Article  CAS  Google Scholar 

  67. Takeuchi, K., Ohga, Y., Ushino, T., and Takasuka, M., J. Phys. Org. Chem., 1997, vol. 10, no. 4, p. 717.

    Article  CAS  Google Scholar 

  68. Abboud, J.-L.M., Alkorta, I., Davalos, J.Z., Muller, P., Quintanilla, E., and Rossier, J.-C., J. Org. Chem., 2003, vol. 68, no. 10, p. 3786.

    Article  CAS  Google Scholar 

  69. Raber, D.J., Harris, J.M., and Schleyer, P.v.R., Ions and Ion Pairs in Organic Reactions, Szwarz, M., Ed., New York: Wiley, 1974, vol. 2, p. 247.

    Google Scholar 

  70. Dvorko, G.F., Evtushenko, N.Yu., and Zhovtyak, V.N., Zh. Obshch. Khim., 1987, vol. 57, no. 5, p. 1157.

    CAS  Google Scholar 

  71. Dvorko, G.F. and Ponomareva, E.A., Org. React. (Tartu), 1985, vol. 22, no. 4, p. 451.

    CAS  Google Scholar 

  72. Sneen, R.A. and Kay, P.S., J. Am. Chem. Soc., 1972, vol. 94, no. 20, p. 6983.

    Article  CAS  Google Scholar 

  73. Kuhn, R. and Trischman, H., Monatsh. Chem., 1964, vol. 95, no. 2, p. 457.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Kiev Polytechnic Institute, National Technical University of Ukraine, pr. Peremogi 37, Kiev, 03056, Ukraine

    N. E. Ponomarev, V. V. Zaliznyi & G. F. Dvorko

Authors
  1. N. E. Ponomarev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. V. V. Zaliznyi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. G. F. Dvorko
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to N. E. Ponomarev.

Additional information

Original Russian Text © N.E. Ponomarev, V.V. Zaliznyi, G.F. Dvorko, 2007, published in Zhurnal Obshchei Khimii, 2007, vol. 77, No. 7, pp. 1120–1130.

For communication XLII, see [1].

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ponomarev, N.E., Zaliznyi, V.V. & Dvorko, G.F. Kinetics and mechanism of monomolecular heterolysis of commercial organohalogen compounds: XLIII. Solvent effect on activation parameters of dehydrochlorination of 3-chloro-3-methylbut-1-ene. Correlation analysis of solvation effects. Russ J Gen Chem 77, 1204–1214 (2007). https://doi.org/10.1134/S1070363207070110

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1070363207070110

Keywords

Search

Navigation