Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Aminolysis of Phenylacetyl Chlorides in Acetonitrile

  • Published : 1998.06.20
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Abstract

The aminolysis reactions of phenylacetyl chlorides with anilines and N,N-dimethylanilines (DMAS) in acetonitrile at -15.0 ℃ are investigated. The magnitude of ρx (= -2.8 ∼ -2.9) and ρy (= 0.9 ∼ 1.3, after correcting for the fall-off), and the negative sign of ρxy (= -0.12) for the reactions with anilines suggest an associative SN2 mechanism. For the reactions with DMAs, the magnitude of these Hammett coefficients increases so that tighter bond making in the transition state (TS) is predicted. A nonlinear Hammett plots obtained for the DMAs with an electron acceptor substituent is interpreted to result from a more advanced degree of leaving group departure to assist closer approach of the bulky DMA in the TS. The normal secondary kinetic isotope effects $(k_H/k_D>1.0)$ involving deuterated anilines suggest partial deprotonation by hydrogen bonding to the departing chloride ion.

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References

  1. Chem. Rev. v.53 Bender, M. L.
  2. Chem. Soc. Rev. v.10 Jencks, W. P.
  3. Chem. Soc. Rev. v.23 Williams, A.
  4. J. Am. chem. Soc. v.106 Palling, D. J.;Jencks, W. P.
  5. J. Chem. Soc. Perkin Trans. v.2 Bond, P. M.;Castro, E. A.;Moodie, R. B.
  6. Zh. Org. Khim. v.17 Litvinenko, L. M.;Shpanko, I. V.;Korostylev, A. P.
  7. Mendeleev Commun Shpanko, I, V.
  8. J. Chem. Soc. Perkin Trans. v.2 Rogne, O.
  9. J. Chem. Soc. Perkin Trans v.2 Lee, I;Shim. C. S.;Chung, S. Y.;Kim, H. Y.;Lee, H. W.
  10. J. Am. Chem. Soc. v.111 Song, B. D.;Jencks, W. P.
  11. J. Chem. Soc. Perkin Trans v.2 Jedrzejczak, M.;Motie, R. E.;Satchell, D. P. N.;Satchell, R. S.;Wassef, W. N.
  12. J. Chem. Soc. Perkin Trans v.2 Yew, K. H.;Koh, H. J.;Lee, H. W.;Lee, I.
  13. Bull. Korean Chem. Soc. v.17 Koh, H. J.;Lee, H. C.;Lee, H. W.;Lee, I.
  14. J. Chem. Soc. Perkin Trans v.2 Kim, T. H.;Huh, C.;Lee, B.-S.;Lee, I.
  15. J. Org. Chem. v.62 Oh, H. K.;Woo, S. Y.;Shin, C. H.;Lee, I.
  16. Int. J. Chem. Oh, H. K.;Lee, J. Y.;Yun, J. H.;Park, Y. S.;Lee, I.
  17. Chem. Soc. Rev. v.24 Lee, I
  18. J. Phys. Org. Chem. v.7 Lee, I;Koh, H. J.;Lee, B. C.
  19. Adv. Phys. Org. Chem. v.27 Lee, I.
  20. The PMO Theory of Organic Chemistry Dewar, M. J. S.;Daugherty, R. C.
  21. J. Am. Chem. Soc. v.97 le Noble, W. J.;Aano, T.
  22. J. Org. Chem. v.44 le Noble, W. J.;Miller, A. R.
  23. J. Phys. Org. Chem. v.3 Lee, I.;Rhys, K. W.;lee, H. W.;Shim, C. S.;Oh, H. K.
  24. J. Chem. Soc. Perkin Trans. v.2 Lee, I.;Koh, H. J.;Lee, H. W.
  25. J. Chem. Soc. Perkin Trans. v.2 Lee, I.;Shin, C. S.;Kim, H. Y.;Lee, H. W.
  26. J. Am. Chem. Soc. v.78 Borawell, F. G.;Boutan, P. J.
  27. Bull. Korean Chem. Soc. v.11 Lee, I.;Koh, H. J.;Lee, B.-S.;Lee, H. W.;Choi, J. H.
  28. Phil. Mag. v.2 Guggenheim, E. A.