52033-51-9Relevant academic research and scientific papers
Solvent Effects on Anchimerically Assisted Solvolyses. II. Solvent Effects in Solvolyses of threo-2-Aryl-1-methylpropyl p-Toluenesulfonates
Fujio, Mizue,Saeki, Yoshihiro,Nakamoto, Kenichiro,Yatsugi, Ken-ichi,Goto, Naomi,et al.
, p. 2603 - 2618 (1995)
The solvent effects on the solvolysis of threo-2-aryl-1-metkhylpropyl p-toluenesulfonates were analyzed with the aid of the extended Winstein-Grunwald Equation.The aryl-assisted kΔ solvolysis of 2-(p-methoxyphenyl)-1-methylpropyl and 2-methyl-2-phenylpropyl p-toluenesulfonates failed to give a single linear correlation with the YOTs parameter.The dispersion against YOTs cannot be due to nucleophilic solvent assistance.The m values from the plots of 2-(p-methoxyphenyl)-1-methylpropyl and 2-methyl-2-phenyl-propyl p-toluenesulfonates against YOTs were significantly lower than m=1.0 for the limiting kc solvolysis.Singificantly improved correlations (R > 0.99; SD Δ scale based on the solvolysis of 2-(p-methoxyphenyl)-2-methylpropyl p-toluenesulfonate, instead of with YOTs.No improvement by the YΔ treatment was obtained for the unsubstituted compound (R=0.97; SD=0.22).A new similarity comparison analysis in terms of YOTs and YΔ, i.e., log (k/k80E)=mcYOTs+mΔYΔ, was applied successfully to the present kΔ solvolyses.The degree of YΔ character relative to the YOTs one, scaled by mΔ/(mc+mΔ), varies for 1-methyl-2-phenylpropyl tosylates in the range from 1.0 to 0.00 in the consistent manner expected if the dispersion in the YOTs plot becomes less pronounced for solvolyses of less significant anchimeric assistance.There is a continuous spectrum of behavior between the extreme pure kc mechanism and the extreme pure kΔ one.
Structural and solvent effects on rates of solvolysis of secondary alkyl substrates - An update
Bentley, T. William,Roberts, Ian
, p. 96 - 100 (2005)
Rate constants for solvolyses of secondary alkyl tosylates in fluorinated media [including hexafluoropropan-2-ol (HFIP), hexafluoroacetone sesquihydrate, and trichloromethylbis(trifluoromethyl)carbinol] are reported. Rates of solvolysis of 2-adamantyl p-toluenesulfonate in 97% (w/w) HFIP-water at 25°C are neither retarded by the addition of NaOTs nor accelerated greatly by NaClO4). The α-deuterium kinetic isotope effect for solvolyses of 1-(1-adamantyl)ethyl methanesulfonate in 20% acetone-water at 25°C is 1.14. Mechanistic implications of these results are discussed. Copyright
