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1,3-Dipolar cycloaddition between substituted phenyl azide and 2,3-dihydrofuran

  • Ahmad Bekhradnia EMAIL logo , Sattar Arshadi and Seyed Siadati
Published/Copyright: October 30, 2013
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Chemical Papers
From the journal Chemical Papers Volume 68 Issue 2

Abstract

A theoretical study was performed on the 1,3-dipolar cycloaddition between 2,3-dihydrofuran and substituted phenyl azide using Density Functional Theory (DFT) in combination with a 6-311++G(d,p) basis set. The optimum geometries for reactant, transition state and product, as well as the kinetic data, rate constants and reaction constant (ρ) were investigated to rationalise the substitution effects and reaction rates of the 1,3-dipolar cycloaddition process in various solvents. The DFT calculation and Frontier Molecular Orbital (FMO) theory as well as the atomic Fukui indices show that the electron-withdrawing substituents enhance the reaction constant (ρ > 0), especially in polar aprotic solvents. Consequently, small changes in the rate constant of the reaction in various solvents and geometric similarity between reactants and transition state structures were suggested as the early transition state mechanism for electron-withdrawing substituents. In addition, the slope of the Hammett plot and susceptibility of the reaction to electron-withdrawing substituents in various solvents confirmed the mechanism.

Keywords: DFT method; substituted phenyl azide; 2,3-dihydrofuran; 1,3-dipolar cycloadditions; Hammett equation; atomic Fukui indices

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Published Online: 2013-10-30
Published in Print: 2014-2-1

© 2013 Institute of Chemistry, Slovak Academy of Sciences

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https://doi.org/10.2478/s11696-013-0440-7
Keywords for this article
DFT method; substituted phenyl azide; 2,3-dihydrofuran; 1,3-dipolar cycloadditions; Hammett equation; atomic Fukui indices

Articles in the same Issue

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  3. Vanadium dodecylamino phosphate: A novel efficient catalyst for synthesis of polyhydroquinolines
  4. Modelling and experimental validation of enantioseparation of racemic phenylalanine via a hollow fibre-supported liquid membrane
  5. Influence of operating conditions on performance of ceramic membrane used for water treatment
  6. Mercury associated with size-fractionated urban particulate matter: three years of sampling in Prague, Czech Republic
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