DOI QR코드

DOI QR Code

The Effect of Solvent on the $\alpha$-Effect(3): Nucleophilic Substitution Reactions of Aryl Acetates in $MeCN-H_2O$ Mixtures of Varying Compositions

  • Um Ik-Hwan (Department of Chemistry, Ewha Womans University) ;
  • Hahn Gee-Jung (Department of Chemistry, Ewha Womans University) ;
  • Lee Gwang-Ju (Department of Chemistry, Ewha Womans University) ;
  • Kwon Dong-Song (Department of Chemistry, Ewha Womans University)
  • Published : 1992.12.20

Abstract

Second-order rate constants have been measured spectrophotometrically for the reactions of substituted phenyl acetates with butane-2,3-dione monoximate and p-chlorophenoxide anions in MeCN-H$_2$O mixtures of varying compositions. The reaction rate, unexpectedly, decreased remarkably upon initial additions of MeCN to H$_2$O up to 30-40 mole ${\%}$ MeCN, and followed by a gradual increase upon further additions of MeCN. The change in solvent composition also influenced the magnitude of the ${\alpha}$-effect, i.e., the ${\alpha}$-effect increased as the mole ${\%}$ MeCN increased. The solvent dependent ${\alpha}$-effect for the present system appears to indicate that the differential solvation between the ${\alpha}$-effect nucleophile and the corresponding normal nucleophile is not solely responsible but the difference in the transition-state stabilization is also responsible for the ${\alpha}$ -effect in organic solvent-rich region.

Keywords

References

  1. J. Am. Chem. Soc. v.84 J. O. Edwards;R. G. pearson
  2. Int. J. Chem. Kinet. v.5 N. J. Fina;J. O. Edwards
  3. Usp. Khim. v.47 A. P. Grekov;V. Y. Veselov
  4. Isr. J. Chem. v.26 E. Buncel;S. Hoz
  5. Catalysis in Chemistry and Enzymology W. P. Jencks
  6. Chemical Reactivity and Reaction Paths R. F. Hudson;Klopman, G.(Ed.)
  7. J. Am. Chem. Soc. v.84 K. M. Ibne-Rasa;J. O. Edwards
  8. J. Org. Chem. v.45 E. Buncel;C. Chuaqui;H. Wilson
  9. J. Org. Chem. v.48 S. Hoz;D. Speizman
  10. J. Am. Chem. Soc. v.86 J. Gerstein;W. P. Jencks
  11. J. Am. Chem. Soc. v.93 J. E. Dixon;T. C. Bruice
  12. J. Am. Chem. Soc. v.80 W. P. Jencks
  13. J. Am. Chem. Soc. v.82 W. P. Jencks;J. Carriuolo
  14. Int. J. Chem. Kinet. v.7 R. Curci;F. Di Furia
  15. J. Am. Chem. Soc. v.99 C. D. Ritchie;R. J. Minasz;A. A. Kamego;M. Sawada
  16. J. Am. Chem. Soc. v.89 M. J. Gregory;T. C. Bruice
  17. J. Am. Chem. Soc. v.77 K. B. Wiberg
  18. J. Am. Chem. Soc. v.112 D. Herschlag;W. P. Jencks
  19. J. Chem. Soc., Chem. Commun R. A. Moss;S. Swarup;S. Ganguli
  20. Peroxide Reaction Mechanisms C. A. Bunton;Edwards, J. O.(Ed.)
  21. Tetrahedron Lett. v.23 S. Wolfe;D. J. Mitchell;H. B. Schlegel;C. Minot;O. Eisenstein
  22. J. Am. Chem. Soc. v.105 H. DePuy;E. W. Della;J. Filley;J. J. Grabowski;V. M. Bierbounm
  23. J. Chem. Soc., Chem. Commun E. Buncel;I. H. Um
  24. Bull. Korean Chem. Soc. v.10 D. S. Kwon;G. J. Lee;I. H. Um
  25. Tetrahedron Lett. v.33 I. H. Um;H. W. Yoon;G. J. Lee;D. S. Kwon
  26. Chem. Rev. v.69 A. J. Parker
  27. J. Am. Chem. Soc. v.98 W.R. Davidson;P. Kebarle
  28. J. Am. Chem. Soc. v.111 S. Ba-Saif;A. K. Luthra;A. William
  29. Bull. Korean Chem. Soc. v.11 D. S. Kwon;G. J. Lee;I. H. Um
  30. Tetrahedron Lett. v.24 E. Buncel;S. Hoz
  31. Rate and Equilibria in Organic Reaction J. E. Leffler;E. Grunwald
  32. Mechanisms of Homogeneous Catalysis from Protons to Proteins M. L. Bender
  33. Trans. Faraday Soc. v.64 D. A. Armitage;M. J. Blandamer;M. J. Foster;N. J. Hidden;K. W. Marcom;M. C. R. Symons;M. J. Wotten
  34. Thermochim. Acta. v.13 C. Moresu;G. Dauhert
  35. J. Chem. Soc., Faraday Trans. I v.72 C. Treiner;P. Tzias;M. Chemla;G. M. Poltoratzkii
  36. Can. J. Chem. v.54 D. F. G-Taylor;D. D. Macdonald
  37. Bull. Chem. Soc. Jpn. v.59 K. Miyaji;K. Morinaga
  38. Bull. Chem. Soc. Jpn. v.56 K. Miyaji;K. Morinage
  39. J. Chem. Soc., Faraday Trans. I v.84 G. Eaton;A. S. Pena-Nunez;M. C. R. Symons
  40. J. Chem. Thermodyn. v.8 C. Moreau;G. Dauheret
  41. Z. Anorg. Chem. v.261 Von A. L. Vierk
  42. J. Am. Chem. Soc. v.105 C. D. Ritchie
  43. Bull. Korean Chem. Soc. v.11 D. S. Kwon;G. J. Lee;I. H. Um
  44. Bull. Korean Chem. Soc. v.12 I. H. Um;J. S. Jeon;D. S. Kwon
  45. Bull. Korean Chem. Soc. v.12 I. H. Um;S. E. Chun;D. S. Kwon
  46. J. Am. Chem. Soc. v.111 E. Buncel;I. H. Um;S. Hoz
  47. J. Am. Chem. Soc. v.90 W. P. Jencks;M. Gilchrist
  48. J. Am. Chem. Soc. v.110 E. Buncel;S. S. Shaik;I. H. Um;S. Wolfe
  49. Ph. D. Thesis I. H. Um
  50. Bull. Korean Chem. Soc. v.11 I. H. Um

Cited by

  1. Effect of Solvent on the &agr;-Effect: Nucleophilic Substitution Reactions of p-Nitrophenyl Acetate with m-Chlorophenoxide and Benzohydroxamates in MeCN−H2O Mixtures of Varying Compo vol.62, pp.17, 1992, https://doi.org/10.1021/jo970665s
  2. Rapid Marcus Curvature Due to Extremely Strong Solvational Imbalances inthe Deprotonation of a Trinitrobenzylic Carbon Acid by Oximate Bases vol.1999, pp.8, 1992, https://doi.org/10.1002/(sici)1099-0690(199908)1999:8<1771::aid-ejoc1771>3.0.co;2-p