ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The rates of reaction of t-BuOOK, t-BuOK, n-BuOOK, and p-MeC6H4OKwith p-nitrophenyl diphenylphosphinate 1 and with p-nitrophenyl benzoate 2 have been measured in toluene both in the absence and in the presence of crown polyether dicyclohexyl-18-crown-6 3a. The rates of nucleophilic displacementon 1 by HOO-, t-BuOO-, and some “nonalpha” oxyanions in water have also been determined. Solvent transfer from water to toluene results in increasing the nucleophilic reactivity of the t-butyl hydroperoxide anion. Rate ratios QQa are given which allow one to estimate the enhanced reactivity of t-BuOO- (an α-nucleophile) compared to oxygen nucleophiles of comparable base strength toward 1 and 2. These are for substrate 1, Qα (water) ≃ 6.5 and Qα (toluene) ≃ 2.7; for substrate 2, Qα (water) ≃ 5.5 and Qα (toluene) ≃ 5. The hypothesis is advanced that solvation is not a major factor in determining the α-effect of the t-butylhydroperoxide anion.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550070304
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