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Kinetic and Molecular Orbital Stuides on the Reaction of 5-nitrofurfural Hydrazone Formation

  • Lee, Kyung-Hee (Department of Chemistry, Teacher's College, Kyungpook National University) ;
  • Jee, Jong-Gi (Department of Chemistry, Teacher's College, Kyungpook National University)
  • Published : 1985.10.20

Abstract

Kinetic measurements of the 5-nitrofurfural-hydrazine reaction in various pH ranges of aquous solution were carried out by ultraviolet spectrophotometry at $25^{\circ},\;35^{\circ}\;and\;45^{\circ}C$. The observed rate of the reaction varies with the change in pH, which gives characteristic "bell-type" rate acidity profile. The maximum rate is shown in the vicinity of pH 4. This reaction procceds with rate-determining attack of hydrazine on the 5-nitrofurfural at low pH and undergoes a change in rate-determining step to dehydration of the addition intermediate as pH increases. The reaction has a "reactant-like transition state" which precedes intermediate in low pH and "product-like transition state" which follows it in neutral pH. The geometry of 5-nitrofurfural-hydrazine intermediate was estimated with PCILO method associated with CNDO/2 scheme.

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References

  1. J. Am. Chem. Soc. v.81 William P. Jancks
  2. J. Am. Chem. Soc. v.94 Jane M. Sayer;Wiliam P. Jencks
  3. J. Am. Chem. Soc. v.95 J. M. Sayer;M. Peskin;W.P. Jencks
  4. Electronic Structure Calculation Gerald A. Segal
  5. Quantum Chemistry Program Exchange
  6. J. Am. Chem. Soc. v.88 no.11 Andrew Williams;Myron L. Bender
  7. An Assoc. Bras. Quim. v.28 no.1-2 Do Amaral;Lucianc Moscovici
  8. J. Am. Chem. Soc. v.90 E. g. Sander;W. P. Jencks
  9. J. Am. Chem. Soc. v.90 W. P. Jencks;M. Gilchrist
  10. J. Am. Chem. Soc. v.82 B. M. Anderson;W.P. Jencks
  11. J. Am. Chem. Soc. v.84 E. H. Cordes;W.P. Jencks
  12. Progr. Phys. Org. Chem. v.2 W.P. Jencks
  13. J. Am. Chem. Soc. v.91 no.23 Jane M. Sayer;Wiliam P. Jenacks