Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Nucleiphilic Substitution Reactions of Thiophenyl Dimethylacetates and Trimethylacetates wkth Benzylamines in Acetonitfile

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Abstract

The kinetics and mechanism of the reactions of thiophenyl dimethylacetates (TDA) and trimethylacetates (TTA) with benzylamines in acetonitrile are studied. The reactions are first order in both the amine and the substrate. Relatively large values of ${\beta}X(\betanuc$ = 1.1-1.5; TDA and 1.1-1.5; TTA) and ${\beta}Z({\beta}lg$ = -1.8~-2.0; DTA and -1.3~-1.6; TTA) for benzylamines, significantly large kH/kD values (=1.2-1.5; DTA and 1.2-1.5; TTA) involving deuterated benzylamines, and large ${\rho}XZ$ (=0.82; TDA and 1.05; TTA) values are interpreted to indicate stepwise acyl transfer mechanism, but with the hydrogen bonded four center type transition state for benzylamine. The relatively greater magnitudes of ${\rho}XZ$ and the secondary kinetic isotope effects involving deuterated nucleophiles are in line with the proposed mechanism.

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References

  1. Chem. Rev. v.85 Jencks, W. P.
  2. Chem. Soc. Rev. v.23 Williams, A.
  3. Am.Chem. Soc. v.99 Gresser, M.;Jenks, W. P.
  4. J. Org. Chem. v.54 Castro, E. A.;Ureta, C.
  5. J. Org. Chem. v.5 Castro, E. A.;Ureta, C.
  6. J. Org. Chem. v.56 Cagrera, M.;Castro, E. A.;Salas, M.;Santos, J. G.;sepulveda, P
  7. J. Am. Chem. Soc. v.99 Hupe, D. J.;Jencks, W. P.
  8. J. Am. Chem. Soc. v.101 Jensin, J. L.;Jencks, W. P.
  9. Acc. Chem. Res. v.54 Dauglass, K. T.
  10. Adv. Phys. Org. Chem. v.27 Lee, I.
  11. Chem. Soc. Rev. v.24 Lee, I.
  12. Adv. Phys. Org. Chem. v.14 Pross, A.
  13. J. Chem. Educ. v.64 Buncelm, E.;Wilsonm H.
  14. J. Org. Chem. v.62 Oh, H. K.;Woo, S. Y.;Shin, C. H.;Park, Y. S.;Lee, J.
  15. Int. J. Chem. Kinet. v.4 Oh, H. K.;Yang, J. H.;Cho, I.;Lee, J.
  16. Prog. Phys. Org. Chem. v.4 Coetzee, J. F.
  17. J. Am. Chem. Soc. v.122 Lee, I. Kim, C. K.;Li, H. G.;Shon, C. K.;Kim. C. K.;Lee, H. W.;Lee, B. S.
  18. Bull. Korean Chem. Soc. v.19 Oh, H. K.;Lee, J. Y.;Lee, I.
  19. Int. J. Chem. Kinet. v.30 Oh, H. K.;Woo, S. Y.;Shin, C. H.;Lee, I.
  20. J. Chem. Soc. Perkin Trans.2 Oh, H. K.;Shin, C. H.;Lee, I.
  21. J. Chem. Soc. Perkin Trans.2 Jedzejczac, M.;Motie, R. E.;Satchell, D. P. N.;Satchell, R. S.;Wassef, W. N.
  22. Phill. Mag. v.2 Guggenhei, E. A.

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