Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Transition-State Variation in the Solvolyses of para-Substiuted Phenyl Chloroformates in Alcohol-Water Mixtures

  • Published : 1998.09.20
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Abstract

Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

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References

  1. Chem. Rev v.60 Bender, M. L
  2. The Chemistry of the Carbonyl Group v.1-2 Patai, S(ed.)
  3. Catalysis in Chemistry and Enzymology Jencks, W. P
  4. Acc. Chem. Res. v.16 Guthrie, J. P
  5. J. Am. Chem. Soc. v.113 Baer, S;Brinkman, E. A;Brauman, J. I
  6. Chem. Soc. Rev. v.23 Williams, A
  7. J. Org. Chem v.48 Yamabe, S;Minato, S
  8. J. Am. Chem. Soc v.109 Blake, J. F;Jorgensen, W. L
  9. J. Am. Chem. Soc v.108 Madura, J. D;Jorgensen, W. L
  10. J. phys. Org. Chem v.8 Park, Y. S;Kim, C. K;Lee, B. S;lee, I;Lim, W. M;Kim, W. K
  11. J. Chem. Soc. Perkin Trans v.2 Bentley, T. W;Jones, R. O
  12. J. Am. Chem. Soc v.111 Song, B. D;Jencks, W. P
  13. The Chemistry of Acyl Halides Kivinen, A;Patai, D(Ed.)
  14. Can. J. Chem v.45 Queen, A
  15. J. Chem. Soc. Perkin Trans v.2 Bentley, T. W;Shim, C. S
  16. J. Chem. Soc. Perkin Trans v.2 Bentley, T. W;Koo, I. S
  17. J. Chem. Soc. Perkin Trans v.2 Jedrzejczak, M;Motie, R. E;Satchell, D. P. N;Satchell, R. S;Wassef, W. N
  18. Reakts. Sposobon. Org. Soedin v.10 shpanko, I. V;Titsku, G. D;Litvinenko, L. M;Eremeev, M. A
  19. Zh. Org. Khim v.17 Litvinenko, L. M;Shpanko, i. V;Korostylev, A. P
  20. Mendeleev Commun v.119 Shpanko, I. V
  21. J. Chem. Soc. Perkin Trans v.2 Rogne, O
  22. J. Chem. Soc. Perkin Trans v.2 Lee, I;Shim, C. S;Chung, S. Y;Kim, H. Y;Lee, H. W
  23. J. Phys. Org. Chem. v.7 Lee, I;Koh, H. J;Lee, B. C
  24. J. Am. Chem. Soc v.111 Song, B. D;Jencks, W. P
  25. J. Chem. Res v.310 Oh, J;Yang, K;Koo, I. S;Lee, I
  26. J. chem. Soc. Perkin Trans v.2 Jedrzejczak, M;Moite, R. E;Satchell, D. P. N
  27. J. Chem. Soc. Perkin Trans v.2 Bentley, T. W;Jones, R. O;Koo, I. S
  28. J. Chem. SOc., Perkin Trans v.2 Exner, O
  29. J. Chem. Soc., Perkin Trans v.2 Bentley, T. W;Carter, G. E;Harris, H. C
  30. J. Chem. Soc. Perkin Trans v.2 Bentley, T. W;harris, H. C
  31. J. Chem. Soc. Chem. Commun v.41 Bentley, T. W;Koo, I. S
  32. Adv. Phys. Org. Chem v.27 Ta-Shma, R;Rappoport, Z
  33. J. Chem. Soc. Perkin Trans v.2 Bentley, T. W;Jones, R. O
  34. Phil. thesis, university of Wales Jones, R. O. M
  35. J. Chem. Soc., Perkin Trans v.2 Bentley, T. W;Ryu, Z. H
  36. J. Am. Chem. Soc. v.103 Pross, A;Shaik, S. S
  37. Bull. Korean Chem. Soc v.7 Lee, I;Song, C. H
  38. J. Chem. Soc. Perkin Trans v.2 Kevill, D. N;D'Souza, M. J
  39. J. Org. Chem v.53 Bentley, T. W;Harris, H. C
  40. J. Chem. Soc. Perkin Trans v.2 Koo, I. S;Bentley, T. W;Kang, D. H;Lee, I.
  41. Tetrahedron v.39 Lee, I;Koo, I. S
  42. Adv. Phys. Org. Chem. v.17 Bentley, T. W;Llewellynm, G
  43. J. Phy. Org. Chem v.6 Koo, I. S;Lee, I;Oh, J;Yang, K;Bentley, T. W.
  44. Bull. Korean Chem. Soc v.18 Koo, I. S;Yang, K;Kang, K;Park, . K;Oh, H. K;Lee, I
  45. Bull. Korean Chem. Soc. v.18 Koo, I. S;Yang, K;Kang, K;Koo, J. C;Park, J. K;Lee, I
  46. J. Chem. Soc., Perkin Trans v.2 Koo, I. S;Yang, K;Kang, K;Lee, I;Bentley, T. W
  47. Bull. korean Chem. Soc v.3 lee, I;Koo,I. S;Shou, S. C;Lee, H. W
  48. The Hammett Equation Johnson, C. D
  49. J. Chem. Soc., Perkin Trans v.2 Oh, H. K;Kwon, Y. B;Cho, I. H;Lee, I
  50. Bull. korean CHem. Soc. v.16 Oh, H. K;Kwon, y. B;Chung, D. S;Lee, I
  51. Chem. Soc. Rev v.24 Lee, I
  52. J. Proc. Roy. Soc v.A284 Murrell, J. M;Randic, M;Williams, D. J
  53. Theoret. Cheim. Acta v.26 Fueno, T;Nagase, S;Tatsumi, K;Yamaguchi, K
  54. Bull. Chem. Soc. Jpn v.41 Fukui, K;Fujimoto, H
  55. J. Chem. Phys v.55 Morokuma, K
  56. Acc. Chem. Res v.10 Kollman, P. A
  57. Prog. Chem. and Chem. Industry v.17 Lee, I