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Rate-Product Correlations for the Solvolysis of 5-Nitro-2-Furoyl Chloride

  • Choi, Ho-June (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Koh, Han-Joong (Department of Science Education, Jeonju National University of Education) ;
  • Ali, Dildar (Institute of Biochemistry, University of Balochistan) ;
  • Yang, Ki-Yull (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Koo, In-Sun (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University)
  • Received : 2012.05.29
  • Accepted : 2012.07.11
  • Published : 2012.10.20
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Abstract

The solvolysis rate constants of 5-nitro-2-furoyl chloride (5-$NO_2(C_4H_2O)$-2-COCl, 1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of $1.20{\pm}0.05$ and $0.37{\pm}0.02$ for l and m, respectively. The activation enthalpies (${\Delta}H^{\neq}$) were 5.63 to $13.0kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -25.9 to $-43.4cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.65 was also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The product selectivity (S) for solvolysis of 1 in alcohol/water mixtures was 1.2 to 11, which is also consistent with the proposed bimolecular reaction mechanism.

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References

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