DOI QR코드

DOI QR Code

Determination of Reactivity by MO Theory (ⅩⅧ). An Intermolecular Perturbation Study of the Acid-Catalyzed Hydrolysis of Diformamide$^*$

  • 발행 : 1980.09.30

초록

Ultraviolet spectrophotometric investigations were carried out on monoalkylbenzene-iodine systems in carbon tetrachloride. The results reveal the formation of one-to-one molecular complexes. On the basis of the equilibrium constants for these complexes of representative monosubstituted benzenes, the following order of increasing stability is obtained: i-propyl- ${\Delta}$H, ${\Delta}$G and ${\Delta}$S for the interaction of a number of monoalkyl substituted benzenes with iodine have been determined. In general, it can be said that as ${\Delta}$H becomes increasingly negative, corresponding decreases in the ${\Delta}$G and the ${\Delta}$S values are observed, and these variations are linear. The thermodynamic constants become increasingly negative with increasing monoalkyl substitution of the aromatic donor nucleus. The complex bond is therefore weak, and its formation is accompanied by relatively small entropy changes. Thus, analysis of these findings is discussed.

키워드

참고문헌

  1. J. Amer. Chem. Soc. v.71 H. A. Benesi;J. H. Hildebrand
  2. J. Korean Chem. Soc. v.77 O. C. Kwun
  3. J. Amer. Chem. Soc. v.77 R. M. Keefer;L. J. Andrews
  4. J. Amer. Chem. Soc. v.72 T. M. Cromwell;R. L. Scott
  5. Trans. Faraday Soc. v.45 K. Hartley;H. A. Skinner
  6. Thesis, University of Amsterdam Solvatie van Jodium in Organische Oplosmiddelen C. van de Stolpe
  7. Chem. Revs. v.54 L. J. Andrews
  8. J. Amer. Chem. Soc. v.73 N. N. Lichtin;P. D. Bartlett
  9. Organic Charge-Transfer Complexes R. Foster
  10. J. Amer. Chem. Soc. v.74 H. C. Brown;J. D. Brady
  11. Rec. Trav. Chem. v.71 J. A. A. Ketelaar;C. van de Stolpe;A. Goudsmit;W. Dzcubas
  12. Re. Trav. Chem. v.69 J. P. Wibaut;E. L. J. Sixma;L. W. F. Kampschmidt;H. Borer
  13. Chem. Commun. R. Foster;C. A. Fyfe;M. I. Foreman
  14. Molecular Complexes in Organic Chemistry L. J. Andrews;R. M. Keefer
  15. Trans. Faraday Soc. v.64 A. H. Ewald
  16. J. Phys. Chem. v.76 A. H. Ewald;J. A. Scudder