Bulletin of the Chemical Society of Japan p. 2603 - 2618 (1995)
Update date:2022-08-16
Topics:
Fujio, Mizue
Saeki, Yoshihiro
Nakamoto, Kenichiro
Yatsugi, Ken-ichi
Goto, Naomi
et al.
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 < 0.14) were obtained for the p-methoxy, 3-chloro-4-methoxy, and p-methyl derivatives with the YΔ 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.
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