DOI QR코드

DOI QR Code

Tightness of the Transition State for the Reactions of Secondary Alkyl Arenesulfonates with Anilines in Acetonitrile

  • Published : 1995.09.20

Abstract

Kinetic studies on the reactions of five secondary acylic alkyl arenesulfonates with anilines are carried out in acetonitrile at 65.0 ℃. The magnitude of ρXZ determined (ρXZ=0.12-0.13) is slightly greater than that for the alicyclic series (ρXZ=0.11) under the same experimental condition. Ab initio MO results are found to support the slightly tighter transition state expected from the greater magnitude of ρXZ for the acyclic series. Despite the small variations, the magnitude of ρXZ and the theoretical transition state tightness remain relatively constant for the secondary carbon centers. Secondary kinetic isotope effects involving deuterated aniline nucleophiles show a successively smaller kH/kD(<1.0) value for a more sterically crowded reaction center carbon. This is in accord with the later transition state for bond-making predicted by the Bell-Evans-Polanyi principle for the more endothermic nucleophilic substitution reaction. Further support is provided by the results of the AM1 MO calculations on the reactions of secondary alkyl benzenesulfonates with chloride nucleophile.

Keywords

References

  1. Chem. Soc. Rev. v.19 Lee, I.
  2. Adv. Phys. Org. Chem. v.27 Lee, I.
  3. J. Chem. Soc. Perkin Trans. 2 Koh, H. J.;Lee, H. W.;Lee. I.
  4. J. Chem. Soc. Perkin Trans. 2 Oh, H. K.;Kwon, Y. B.;Cho, I. H.;Lee. I.
  5. J. Org. Chem. v.59 Lee, I.;Kim, C. K.;Chung, D. S.;Lee, B-S.
  6. J. Chem. Res. Lee, I.;Koh, H. J.;Lee, H. W.
  7. J. Chem. Res. Lee, I.;Koh, H. J.;Lee, H. W.
  8. J. Chem. Soc., Perkin Trans. 2 Lee, I.;Koh, H. J.;Lee, B-S.;Sohn, D. S.;Lee, B. C.
  9. J. Am. Chem. Soc. v.98 Bentley, T. W.;Schleyer, P. v. R.
  10. Int. J. Quant. Chem. v.S13 Pople, J. A.;Krishnan, R.;Schegel, H. B.;Binkley, J. S.
  11. Int. J. Quant. Chem. v.S15 Pople, J. A.;Schlegel, H. B.;Krishnan, R. D.;Defrees, J.;Binkley, J. S.;Frisch, M. J.;Whiteside, R. A.;Hout, R. F.;Hehre, W. J.
  12. Gaussian 92(Revision C.) Frich, M. J.;Trucks, G. W.;Head-Gordon, M.;Gill, P. M. W.;Wong, M. W.;Foresmam, J. B.;Johnson, B. G.;Schlegel, H. B.;Robb, M. A.;Replogle, E. S.;Gomperts, R.;Andres, J. L;Raghavachari, K.;Binkley, J. S.;Gonzalez, C.;Martin, R. L.;Fox, D. J.;Defress, D. J.;Baker, J.;Stewart, J. J. P.;Pople, J. A.
  13. Tetrahedron v.49 Chung, D. S.;Kim, C. K.;Lee, B-S.;Lee, I.
  14. Steric Effects in Organic Chemistry Taft, R. W.;Newman, M.(ed.)
  15. Ab Inito Molecular Orbital Theory Hehre, W. J.;Radom, L.;Schleyer, P. v. R.;Pople, J. A.
  16. Theoretical Aspects of Physical Organic Chemistry. The $S_N2$ Mechanism Shaik, S. S.;Schlegel, H. B.;Wolfe, S.
  17. J. Am. Chem. Soc. v.97 le Noble, W. J.;Asano, T.
  18. J. Org. Chem. v.44 le Noble, W. J.;Miller, A. R.
  19. The PMO Theory of Organic Chemistry Dewar, M. J. S.;Dougherty, R. C.
  20. J. Am. Chem. Soc. v.107 Dewar, M. J. S.;Zoebisch, E. G.;Healy, E. F.;Stewart, J. J. P.
  21. QCPE Bull. v.6 AMPAC : Austin Model 1 Pakage, (QCPE 506) Dewar, M. J. S.;Stewart, J. J. P.