Skip to main content
SpringerLink
Log in

Reactivity Variation of Tetracyanoethylene and 4-Phenyl-1,2,4-Triazoline-3,5-Dione in Cycloaddition Reactions in Solutions

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

The reasons for the very high reactivity and variability of reactivity of two dienophiles, tetracyanoethylene (1) and 4-phenyl-1,2,4-triazoline-3,5-dione (2), in the Diels–Alder reactions were considered. The data on the rate of reactions with anthracene (3), benzanthracene (4) and dibenzanthracene (5) in 14 solvents over a range of temperatures and high pressures, data on the change in the enthalpy of solvation of reagents, transition state, and adducts in the forward and backward reactions, and the enthalpies of these reactions in solution were obtained. Strong π-acceptor dienophile 1 has sharply reduced reactivity in reactions in π-donor aromatic solvents. It was observed that the π-acceptor properties of dienophile 1 disappear upon passage to the transition state and adduct. Large solvent effects on the reaction rate can be predicted for all types of reactions involving tetracyanoethylene. Very high reactivity of dienophiles 1 and, especially, 2 can be useful to catch such carcinogenic impurities such as 3–5 and neutralize them by transformation into less dangerous adducts.

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

Scheme 1
Fig. 1
Fig. 2

Similar content being viewed by others

References

  1. Fringuelli, F., Taticchi, A.: The Diels–Alder Reaction: Selected Practical Methods. Wiley, New York (2002)

    Google Scholar 

  2. Kobayashi, S., Jorgensen, K.A.: Cycloaddition Reaction in Organic Synthesis. Wiley, New York (2001)

    Book  Google Scholar 

  3. Kiselev, V.D., Konovalov, A.I.: Internal and external factors influencing the Diels–Alder reaction. J. Phys. Org. Chem. 22, 466–483 (2009)

    Article  CAS  Google Scholar 

  4. Sauer, J., Sustmann, R.: Mechanistic aspects of Diels–Alder reactions: a critical survey. Angew. Chem. Int. Ed. 19, 779–807 (1980)

    Article  Google Scholar 

  5. Woodward, R.B., Hoffmann, R.: The concervation of orbital symmetry. Angew. Chem. Int. Ed. 8, 781–932 (1969)

    Article  CAS  Google Scholar 

  6. 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)

    Article  CAS  Google Scholar 

  7. Narayan, S., Muldoon, J., Finn, M.G., Fokin, V.V., Kolb, H.C., Sharpless, K.B.: “On water”: unique reactivity of organic compounds in aqueous suspension. Angew. Chem. Int. Ed. 44, 3275–3279 (2005)

    Article  CAS  Google Scholar 

  8. Kiselev, V.D., Shakirova, I.I., Kornilov, D.A., Kashaeva, H.A., Potapova, L.N., Konovalov, A.I.: Homo-Diels–Alder reaction of a very inactive diene, bicyclo[2,2,1]hepta-2,5-diene, with the most active dienophile, 4-phenyl-1,2,4-triazoline-3,5-dione. Solvent, temperature, and high pressure influence on the reaction rate. J. Phys. Org. Chem. 26, 47–53 (2013)

    Article  CAS  Google Scholar 

  9. Houk, K.N., Munchausen, L.L.: Ionization potentials, electron affinities, and reactivities of cyanoalkenes and related electron-deficient alkenes. A frontier molecular orbital treatment of cyanoalkene reactivities in cycloaddition, electrophilic, nucleophilic, and radical reactions. J. Am. Chem. Soc. 98, 937–946 (1976)

    Article  CAS  Google Scholar 

  10. Rücker, C., Lang, D., Sauer, J., Friege, H., Sustmann, R.: Reaktivität substituierter 1,3-butadiene in Diels–Alder-Reaktionen. Chem. Ber. 113, 1663–1690 (1980)

    Article  Google Scholar 

  11. Cookson, R.C., Gilani, S.S.H., Stevens, I.D.R.: 4-Phenyl-1,2,4-triazolin-3,5-dione: a powerful dienophile. Tetrahedron Lett. 3, 615–618 (1962)

    Article  Google Scholar 

  12. Kiselev, V.D., Kornilov, D.A., Lekomtseva, I.I., Konovalov, A.I.: Reactivity of 4-phenyl-1,2,4-triazoline-3,5-dione and diethylazocarboxylate in [4 + 2]-cycloaddition and ene reactions: solvent, temperature, and high-pressure influence on the reaction rate. Int. J. Chem. Kinet. 47, 289–301 (2015)

    Article  CAS  Google Scholar 

  13. Sauer, J., Schröder, B.: Eine Studie der Diels–Alder-Reaktions, VIII. 4-Phenyl-1.2.4-triazolin-dion-(3.5) als Dienophil. Chem. Ber. 100, 678–684 (1967)

    Article  CAS  Google Scholar 

  14. Breton, G.W., Newton, K.A.: Further studies of the thermal and photochemical Diels–Alder reactions of N-methyl-1,2,4-triazoline-3,5-dione (MeTAD) with naphthalene and some substituted naphthalenes. J. Org. Chem. 65, 2863–2869 (2000)

    Article  CAS  PubMed  Google Scholar 

  15. Riddick, J.A., Bunger, W.B., Sakano, T.K.: Organic Solvents, 4th edn. Wiley, New York (1986)

    Google Scholar 

  16. Kiselev, V.D., Kornilov, D.A., Anikin, O.V., Sedov, I.A., Konovalov, A.I.: Kinetics and thermochemistry of the unusual [2π + 2σ + 2σ]-cycloaddition of quadricyclane with some dienophiles. J. Phys. Org. Chem. 31, e3737 (2017). https://doi.org/10.1002/poc.3737

    Article  CAS  Google Scholar 

  17. Kornilov, D.A., Kiselev, V.D.: New approach to determine the activation and reaction volumes of low polar molecular processes. Int. J. Chem. Kinet. 47, 389–394 (2015)

    Article  CAS  Google Scholar 

  18. Kiselev, V.D.: High-pressure influence on the rate of Diels–Alder cycloaddition reactions of maleic anhydride with some dienes. Int. J. Chem. Kinet. 45, 613–622 (2013)

    Article  CAS  Google Scholar 

  19. Kiselev, V.D., Bolotov, A.V., Satonin, A., Shakirova, I., Kashaeva, H.A., Konovalov, A.I.: Compressibility of liquids. Rule of noncrossing V-P curvatures. J. Phys. Chem. B 112, 6674–6682 (2008)

    Article  CAS  PubMed  Google Scholar 

  20. Kiselev, V.D., Kashaeva, E.A., Luzanova, N.A., Konovalov, A.I.: Enthalpies of solution of lithium perchlorate and Reichardt’s dye in some organic solvents. Thermochim. Acta 303, 225–228 (1997)

    Article  CAS  Google Scholar 

  21. Gayer, K.H., Kothari, P.S.: Enthalpies of solution of potassium chloride and 2-amino-2-(hydroxymethyl) 1,3-propanediol. Thermochim. Acta 15, 301–305 (1976)

    Article  CAS  Google Scholar 

  22. Rogers, F.E.: Thermochemistry of the Diels–Alder reactions. II. Heat of addition of several dienes to tetracyanoethylene. J. Phys. Chem. 76, 106–109 (1972)

    Article  CAS  Google Scholar 

  23. Brown, P., Cookson, R.S.: Kinetics of addition of tetracyanoethylene to anthracene and bicyclo[2,2,1]heptadiene. Tetrahedron 21, 1977–1991 (1965)

    Article  CAS  Google Scholar 

  24. 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)

    Article  CAS  Google Scholar 

  25. Radomska, M., Radomski, R.: Phase diagrams in the binary systems of tetracyanoethylene with mesitylene, durene and pentamethylbenzene. J. Therm. Anal. 37, 693–704 (1991)

    Article  CAS  Google Scholar 

  26. Merrifield, R.E., Phillips, W.D.: Cyanocarbon chemistry. II. Spectroscopic studies of the molecular complexes of tetracyanoethylene. J. Am. Chem. Soc. 80, 2778–2782 (1958)

    Article  Google Scholar 

  27. Brown, R.D.: A theoretical treatment of the Diels–Alder reaction. Part I. Polycyclic aromatic hydrocarbons. J. Chem. Soc. (1950). https://doi.org/10.1039/JR9500000691

    Article  Google Scholar 

  28. 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)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We are grateful to Dr. Igor Sedov for carrying out some calorimetric measurements. This work was supported by the Russian Foundation for Basic Research (Projects Nos. 16-03-00071 and 18-33-00063), the Ministry of Education and Science of Russian Federation (Project No. 4.6223.2017/9.10), and the research grant of Kazan Federal University.

Author information

Authors and Affiliations

  1. Laboratory of High Pressure Chemistry, Butlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya Str., 18, Kazan, Russian Federation, 420008

    Vladimir D. Kiselev, Dmitry A. Kornilov, Oleg V. Anikin & Alexey A. Shulyatiev

  2. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of Russian Academy of Sciences, Kazan, Russian Federation, 420088

    Alexander I. Konovalov

Authors
  1. Vladimir D. Kiselev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dmitry A. Kornilov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Oleg V. Anikin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Alexey A. Shulyatiev
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Alexander I. Konovalov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Vladimir D. Kiselev.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kiselev, V.D., Kornilov, D.A., Anikin, O.V. et al. Reactivity Variation of Tetracyanoethylene and 4-Phenyl-1,2,4-Triazoline-3,5-Dione in Cycloaddition Reactions in Solutions. J Solution Chem 48, 31–44 (2019). https://doi.org/10.1007/s10953-019-00846-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-019-00846-6

Keywords

Search

Navigation