Premium
Reactivity of sodium arenesulfinates in the substitution reaction to γ ‐functionalized allyl bromides
Author(s) -
Khamis Galina,
Stoeva Stoyanka,
Aleksiev Dimitar
Publication year - 2010
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1629
Subject(s) - chemistry , enthalpy , reactivity (psychology) , nucleophilic substitution , nucleophile , substitution reaction , kinetic energy , kinetics , entropy of activation , medicinal chemistry , ion , sodium , reaction rate constant , standard enthalpy of formation , inorganic chemistry , organic chemistry , thermodynamics , catalysis , alternative medicine , pathology , medicine , physics , quantum mechanics
The kinetics of nucleophilic bimolecular substitution reactions of γ ‐functionalized allyl bromides with non‐substituted and p ‐substituted sodium arenesulfinates has been studied. Both the structure of allyl bromides and nucleophilicity of arenesulfinate ions exerted a significant effect on the values of the kinetic parameters such as the second‐order rate constants k , activation energy E A , and changes in the entropy Δ S ≠ , enthalpy Δ H ≠ , and free energy Δ G ≠ of the formation of the activated complex from reactants. Based on the evaluation of kinetic parameters, the reactants could be arranged, according to their decreasing reactivity in the S N 2‐reactions as follows: p ‐toluenesulfinate ion > benzenesulfinate ion > p ‐chlorobenzenesulfinate ion and 4‐bromo‐2‐butenenitrile > 1,3‐ dibromopropene, respectively. Comparison was also made between the kinetic data obtained and some delocalization reactivity indexes for both the substrates and nucleophiles. The enthalpy–entropy compensation effect was observed for the reactions of sodium arenesulfinates with γ ‐functionalized allyl bromides. Copyright © 2009 John Wiley & Sons, Ltd.