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Journal of Solution Chemistry

, Volume 41, Issue 3, pp 525–535 | Cite as

Anomalies in the Change of Volumetric Parameters of the Diels–Alder Reaction in Solution

  • Vladimir D. Kiselev
  • Alexander V. Bolotov
  • Ilzida I. Shakirova
  • Helen A. Kashaeva
  • Lubov N. Potapova
  • Alexander I. Konovalov
Article

Abstract

In this article negative values of the activation volume in retro-Diels–Alder reactions are interpreted in terms of the different possibilities of penetration of the solvent molecules into the sterically branched structures of the adduct and activated complex. Empty spaces, inaccessible to penetration of solvent molecules, lead to increases of the molar volume of the screened adducts in solution and, consequently, to a less negative value of the Diels–Alder reaction volume. The values of partial molar volumes of anthracene, maleic anhydride and the adducts cyclopentadiene–maleic anhydride, anthracene–maleic anhydride and anthracene–tetracyanoethylene, in several solvents, were calculated from the solution density data.

Keywords

Diels–Alder reaction Solvent effect Reaction volume Partial molar volume Intramolecular holes 

Notes

Acknowledgements

This work was supported by the Russian Federal Agency of Education (No P-2345, GK No 14.740.11.0377, GK No OK-1/2010). We also appreciate fruitful comments from the reviewers, which helped for us in finalizing this manuscript.

References

  1. 1.
    Isaacs, N.S.: Liquid Phase High Pressure Chemistry. Wiley-Interscience, Chichester (1981). Chap. 2 Google Scholar
  2. 2.
    le Noble, W.J.: Organic High Pressure Chemistry. Elsevier, Amsterdam (1988) Google Scholar
  3. 3.
    Wurche, F., Klärner, F.-G.: High Pressure Chemistry. Wiley-VCH, Weinheim (2002). Chap. 2 Google Scholar
  4. 4.
    Kiselev, V.D., Konovalov, A.I.: Internal and external factors influencing the Diels–Alder reaction. J. Phys. Org. Chem. 22, 466–483 (2009) CrossRefGoogle Scholar
  5. 5.
    Asano, T., le Noble, W.J.: Activation and reaction volumes in solution. Chem. Rev. 78, 407–489 (1978) CrossRefGoogle Scholar
  6. 6.
    van Eldik, R., Asano, T., le Noble, W.J.: Activation and reaction volumes in solution. 2. Chem. Rev. 89, 549–688 (1989) CrossRefGoogle Scholar
  7. 7.
    Drljaca, A., Hubbard, C.D., van Eldik, R., Asano, T., Basilevsky, M.A., le Noble, W.J.: Activation and reaction volumes in solution. 3. Chem. Rev. 98, 2167–2289 (1998) CrossRefGoogle Scholar
  8. 8.
    Kiselev, V.D., Kashaeva, E.A., Konovalov, A.I.: Pressure effect on the rate and equilibrium constants of the Diels–Alder reaction 9-chloroanthracene with tetracyanoethylene. Tetrahedron 55, 1153–1162 (1999) CrossRefGoogle Scholar
  9. 9.
    Sauer, J., Sustmann, R.: Mechanistic aspects of Diels–Alder reactions: a critical survey. Angew. Chem. 92, 773–801 (1980) CrossRefGoogle Scholar
  10. 10.
    Sauer, J., Sustmann, R.: Angew. Chem. Int. Ed. 19, 779–807 (1980) CrossRefGoogle Scholar
  11. 11.
    Kiselev, V.D.: Why can the activation volume of the cycloadduct decomposition in isopolar retro-Diels–Alder reactions be negative? Int. J. Chem. Kinet. 42, 117–125 (2010) CrossRefGoogle Scholar
  12. 12.
    Kiselev, V.D., Miller, J.G.: Experimental proof that the Diels–Alder reaction of tetracyanoethylene with 9,10-dimethylanthracene passes through formation of a complex between the reactants. J. Am. Chem. Soc. 97, 4036–4039 (1975) CrossRefGoogle Scholar
  13. 13.
    Kiselev, V.D., Kashaeva, E.A., Shihab, M.S., Medvedeva, M.D., Konovalov, A.I.: Dramatic solvent effect on the volume of the Diels–Alder reaction between tetracyanoethylene and cyclopentadiene. Russ. Chem. Bull. Int. Ed. 49, 1040–1044 (2000) CrossRefGoogle Scholar
  14. 14.
    Kiselev, V.D., Konovalov, A.I., Asano, T., Iskhakova, G.G., Kashaeva, E.A., Shihab, M.S., Medvedeva, M.D.: Solvent effect on the volume of activation and volume of the Diels–Alder reaction. J. Phys. Org. Chem. 14, 636–643 (2001) CrossRefGoogle Scholar
  15. 15.
    Klärner, F.-G., Breitkopf, V.: The effect of pressure on retro Diels–Alder reactions. Eur. J. Org. Chem. 11, 2757–2762 (1999) CrossRefGoogle Scholar
  16. 16.
    Jenner, G., Papadopoulos, M., Rimmelin, J.: Activation parameters and location of the transition state in the retro-Diels–Alder reaction of a 7-oxabicylo[2.2.1]hept-5-ene derivative. J. Org. Chem. 48, 748–749 (1983) CrossRefGoogle Scholar
  17. 17.
    George, A.V., Isaacs, N.S.: Reactions at high pressure. Part 15. Rates, activation parameters, and a volume profile for retro-Diels–Alder reactions in the pyrrole series. J. Chem. Soc., Perkin Trans. 2, 1845–1848 (1985) Google Scholar
  18. 18.
    Grieger, R.A., Eckert, C.A.: Solvent effects on the activation volume of a Diels–Alder reaction. Trans. Faraday Soc. 66, 2579–2584 (1970) CrossRefGoogle Scholar
  19. 19.
    McCabe, J.R., Eckert, C.A.: High-pressure kinetic studies of solvent and substituent effects on Diels–Alder reactions. Ind. Eng. Chem. Fundam. 13, 168–172 (1974) CrossRefGoogle Scholar
  20. 20.
    Klärner, F.-D., Dietrich, M.K.: Chemistry of Dienes and Polyenes, vol. 1. Wiley, London (1997) Google Scholar
  21. 21.
    Jenner, G.: High-pressure mechanistic delineation based on activation volumes. J. Phys. Org. Chem. 15, 1–16 (2002) CrossRefGoogle Scholar
  22. 22.
    El’yanov, B.S., Gonigberg, E.: Effect of pressure and temperature on some kinetic and thermodynamic parameters of non-ionic reactions. Volume changes on activation and reaction. J. Chem. Soc. Faraday Trans. I 75, 172–175 (1979) CrossRefGoogle Scholar
  23. 23.
    David, R.L., Frederikse, H.P.R.: Handbook of Chemistry and Physics, 75th edn. CRC Press, Boca Raton (1994–1995) Google Scholar
  24. 24.
    Craig, D.: The rearrangement of endo-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalic anhydride. J. Am. Chem. Soc. 73, 4889–4892 (1951) CrossRefGoogle Scholar
  25. 25.
    Riddick, J.A., Bunger, W.B., Sakano, T.K.: Organic Solvents, 4th edn. Wiley-Interscience, New York (1986) Google Scholar
  26. 26.
    Kiselev, V.D., Iskhakova, G.G., Kashaeva, E.A., Potapova, L.N., Konovalov, A.I.: Diels–Alder reaction volumes in the solid state and solution. Russ. Chem. Bull. Int. Ed. 53, 2490–2495 (2004) CrossRefGoogle Scholar
  27. 27.
    Millero, F.: Molal volumes of electrolytes. Chem. Rev. 71, 147–176 (1971) CrossRefGoogle Scholar
  28. 28.
    Marcus, Y., Hefter, G.: Standard partial molar volumes of electrolytes and ions in nonaqueous solvents. Chem. Rev. 104, 3405–3452 (2004) CrossRefGoogle Scholar
  29. 29.
    Kiselev, V.D., Kashaeva, E.A., Iskhakova, G.G., Potapova, L.N., Konovalov, A.I.: Solvent effect on the heat of solution and partial molar volume of some non-electrolytes and lithium perchlorate. J. Phys. Org. Chem. 19, 179–186 (2006) CrossRefGoogle Scholar
  30. 30.
    Kiselev, V.D., Bolotov, A.V., Satonin, A.P., Shakirova, I.I., Averyanova, A.D., Kashaeva, H.A., Konovalov, A.I.: Solvent effect on the heat of solution and partial molar volume of magnesium perchlorate. J. Phys. Org. Chem. 24, 29–37 (2011) CrossRefGoogle Scholar
  31. 31.
    Kiselev, V.D., Kashaeva, E.A., Bolotov, A.V., Shakirova, I.I., Konovalov, A.I.: Energy and volume activation parameters of the retro-Diels–Alder reaction in different solvents. Russ. Chem. Bull. Int. Ed. 58, 21–24 (2009) CrossRefGoogle Scholar
  32. 32.
    Ruelle, P., Farina-Cuendet, A., Kesselring, U.W.: Changes of molar volume from solid to liquid and solution: the particular case of C60. J. Am. Chem. Soc. 118, 1777–1784 (1996) CrossRefGoogle Scholar
  33. 33.
    Smith, A.L., Walter, E., Korobov, M., Gurvich, O.L.: Some enthalpies of solution of C60 and C70. Thermodynamics of the temperature dependence of fullerene solubility. J. Phys. Chem. 100, 6775–6780 (1996) CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Vladimir D. Kiselev
    • 1
  • Alexander V. Bolotov
    • 1
  • Ilzida I. Shakirova
    • 1
  • Helen A. Kashaeva
    • 1
  • Lubov N. Potapova
    • 1
  • Alexander I. Konovalov
    • 1
  1. 1.Department of Physical Chemistry, Butlerov Institute of ChemistryKazan Federal UniversityKazanRussian Federation

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