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Rate and Equilibrium Constants for Reactions Transferring a Dimethylcarbamoyl Group between Pyridines

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Abstract

We have studied 18 reactions, including four identity reactions, involving transfer of a dimethylcarbamoyl group with N-acylpyridinium bonds to pyridine and its 4-substituted derivatives in acetonitrile solutions at 298 K. The rate constants k ij varied within the range 0.4 to 10−6 L/mol·s; the equilibrium constants K ij varied from 107 to 10−5. The rate and equilibrium for exchange of carbamoyl groups are described satisfactorily by the Brönsted equation. We have shown that all the reactions occur according to a forced concerted S N2 mechanism. The structure of the transition state and its position on the reaction coordinate for identity transfer are considered using a More O'Ferrall-Jencks diagram.

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REFERENCES

  1. V. I. Rybachenko, G. Schroeder, K. Yu. Choty, and V. V. Kovalenko, Teor. Éksp. Khim., 34, No. 2, 96-102 (1998).

    Google Scholar 

  2. V. I. Rybachenko, G. Schroeder, B. Leska, et al., Teor. Éksp. Khim., 33, No. 3, 143-148 (1997).

    Google Scholar 

  3. E. V. Titov, R. A. Makarova, V. I. Rybachenko, et al., Teor. Éksp. Khim., 24, No. 2, 227-232 (1988).

    Google Scholar 

  4. V. I. Rybachenko, G. Schroeder, K. Yu. Choty, et al., Teor. Éksp. Khim., 36, No. 6, 363-366 (2000).

    Google Scholar 

  5. A. Williams, Chem. Soc. Rev., 23, No. 1, 93-100 (1994).

    Google Scholar 

  6. S. S. Shaik, H. B. Schlegel, and S. Wolfe, Theoretical Aspects of Physical Organic Chemistry. The SN2 Mechanism, Wiley, New York (1992).

    Google Scholar 

  7. V. A. Savelova and N. M. Oleinik, Mechanisms of Action of Organic Catalysts [in Russian], Naukova Dumka, Kiev (1990).

    Google Scholar 

  8. R. A. More O'Ferrall, J. Chem. Soc. B., No. 2, 274-277 (1970).

  9. D. A. Jencks and W. P. Jencks, J. Am. Chem. Soc., 94, No. 24, 7498-7960 (1977).

    Google Scholar 

  10. M. M. Kreevoy and I.-S.H. Lee, J. Am. Chem. Soc., 106, No. 9, 2550-2553 (1984).

    Google Scholar 

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Authors and Affiliations

  1. L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Luxemburg Vul., 83114, Donets'k, Ukraine

    V. I. Rybachenko, K. Yu. Chotii & V. V. Kovalenko

  2. Chemistry Department, Adam Mickiewicz University, 6 Grunwaldska Str., 60-780, Poznan, Poland

    G. Schroeder & K. Eitner

Authors
  1. V. I. Rybachenko
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  2. G. Schroeder
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  3. K. Yu. Chotii
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  4. V. V. Kovalenko
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  5. K. Eitner
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Rybachenko, V.I., Schroeder, G., Chotii, K.Y. et al. Rate and Equilibrium Constants for Reactions Transferring a Dimethylcarbamoyl Group between Pyridines. Theoretical and Experimental Chemistry 37, 230–235 (2001). https://doi.org/10.1023/A:1012524427859

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