61657-42-9Relevant academic research and scientific papers
Using Kamlet-Taft solvent descriptors to explain the reactivity of anionic nucleophiles in ionic liquids
Crowhurst, Lorna,Falcone, Ruben,Lancaster, N. Llewellyn,Llopis-Mestre, Veronica,Welton, Tom
, p. 8847 - 8853 (2006)
In this paper, we report the effect of ionic liquids on substitution reactions using a variety of anionic nucleophiles. We have combined new studies of the reactivity of polyatomic anions, acetate, trifuoroacetate, cyanide, and thiocyanide, with our previous studies of the halides in [C4C 1Py][Tf2N], [C4C1py][TfO], and [C4C1im][Tf2N] (where [C4C 1im]+ is 1-butyl-3-methylimidazolium and [C 4C1py]+ is 1-butyl-1-methylpyrrolidinium) and compared their reactivities, k2, to the same reactions in the molecular solvents dichloromethane, dimethylsulfoxide, and methanol. The Kamlet-Taft solvent descriptors (α, β, π*) have been used to analyze the rates of the reactions, which were found to have a strong inverse dependency on the α value of the solvent. This result is attributed to the ability of the solvent to hydrogen bond to the nucleophile, so reducing its reactivity. The Eyring activation parameters (ΔH? and ΔS?), while confirming the reaction mechanism, do not offer obvious correlations with the Kamlet-Taft solvent descriptors.
CORRELATION OF THE RATES OF REACTION OF ARENESULFONATE IONS WITH THE TRIMETHYLOXONIUM ION IN ACETONITRILE
Kevill, Dennis N.,Lin, Gloria Meichia L.,Wang, An
, p. 715 - 717 (2007/10/02)
The kinetics of the reactions between trimethyloxonium hexafluorophosphate and a series of tetra-n-butylammonium arenesulfonates have been studied in acetonitrile at -23.4 deg C.With the oxonium salt concentration at about 0.01 M, two series of runs were carried out; Hammett plots of the second-order rate coefficients led to ρ values of -1.18 +/- 0.04 for 0.04 M arenesulfonate salt and -1.07 +/- 0.02 for 0.16 M arenesulfonate salt.Solvolysis kinetics for the trimethyloxonium ion in acetonitrile are also reported.
