Bulletin of the Korean Chemical Society

  • 제7권4호
  • /
  • Pages.279-282
  • /
  • 1986
  • /
  • 0253-2964(pISSN)
  • /
  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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MO Studies on the Gas-Phase Reaction of Dypnone Oxide with Chloride Ion$^\dag$

  • Kim, Wang-Ki (Department of Chemistry, Education, Chonnam National University) ;
  • Sohn, Chang-Kook (Department of Chemistry, Education, Chonnam National University) ;
  • Lee, Ik-Choon (Department of Chemistry, Inha University)
  • 발행 : 1986.08.20
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초록

The MNDO calculations were performed in order to investigate the gas-phase reaction mechanism of 2-propene-1-al oxide, as a model compound of dypnone oxide(1,3-diphenyl-2-butene-1-one oxide) with the chloride ion. Optimized geometries and heats of formation for two probable concerted pathways, CHO and H migration, were determined and their activation energies were obtained. MO results show that although the formyl migration is thermodynamically more favorable than the hydride migration, the latter kinetically predominates over the formyl migration, which is contrary to the established migrating preferences. It is concluded that the hydride migratory propensity is catalyzed by the chloride ion by reducing the capability of the carbonyl ${\pi}$ bond to participate in the migration.

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참고문헌

  1. Chem. Rev. v.59 R.E. Parker;N.S. Isaacs
  2. Tetrahedron Lett. J.P. Nagarkatti;K.R. Ashley
  3. J. Am. Chem. Soc. v.76 H.O. House
  4. J. Am. Chem. Soc. v.83 H.O. House;J.D. Ryerson
  5. J. Org. Chem. v.49 R.D. Bach;J.M. Domagala
  6. J. Am. Chem. Soc. v.99 M.J.S. Dewar;W. Thiel
  7. Angew. Chem. Int. Ed. Engl. v.19 K. Muller
  8. J. Am. Chem. Soc. v.94 J.W. Mclver, Jr.;A. Komonichi
  9. J. Chem. Soc. J.K. Addy;R.E. Parker
  10. J. Chem. Soc. v.B J. Biggs;N.B. Chapman;A.F. Finch;V. Wray
  11. Adv. Phys. Org. Chem. v.15 J. Hine
  12. The MO Theory of Organic Chemistry M.J.S. Dewar
  13. Record Chem. Prog. v.15 Stereochemical Control of Organic Reactions D.Y. Curtin
  14. J. Am. Chem. Soc. v.98 J. Kagan;D.A. Agdeppa;S.P. Singh;D.A. Meyers;C. Bayajian;C. Pourker;B.E. Firth
  15. J. Am. Chem. Soc. v.86 K.L. Servis;J.D. Roberts