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- W2011452828 abstract "A kinetic study is reported for nucleophilic substitution reactions of O-Y-substituted phenyl thionobenzoates (1a−h) and O-4-nitrophenyl X-substituted thionobenzoates (2a−f) with N3− and CN− in 80 mol % H2O−20 mol % DMSO at 25.0 ± 0.1 °C. The Brønsted-type plot for the reactions of 1a−h with N3− exhibits a downward curvature, i.e., the slope (βlg) changes from −1.10 to −0.33 as the leaving group basicity decreases, indicating that the reactions proceed through a stepwise mechanism with a change in rate-determining step (RDS). In contrast, the Brønsted-type plot for the corresponding reactions with CN− is linear with a βlg value of −0.33. This value is similar to that found previously for the reactions of 1a−h with OH− (−0.35). Besides, σo constants result in much better Hammett correlation than σ− constants. Thus, the reactions with CN− and OH− have been concluded to proceed through a stepwise mechanism in which departure of the leaving group occurs after RDS. Reactions of 2a−f with N3− and CN− result in nonlinear Hammett plots. However, the Yukawa−Tsuno plots for the same reactions exhibit excellent linearity with r = 0.5 ± 0.1, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by ground state stabilization through resonance interactions between the electron-donating substituent and the thio carbonyl functionality. Calculation of the k1 values (nucleophile attack as RDS) for the reactions of 1a−h with N3− indicates that azide ion is more reactive than OH− toward the thione esters, although the former is over 11 pKa units less basic than the latter. The high polarizability of N3− has been suggested to be responsible for its great affinity for the polarizable thione esters 1a−h and 2a−f." @default.
- W2011452828 created "2016-06-24" @default.
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- W2011452828 creator A5035870764 @default.
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- W2011452828 date "2009-01-02" @default.
- W2011452828 modified "2023-09-27" @default.
- W2011452828 title "Kinetic Studies on Nucleophilic Substitution Reactions of <i>O</i>-Aryl Thionobenzoates with Azide, Cyanide, and Hydroxide: Contrasting Reactivity and Mechanism" @default.
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- W2011452828 doi "https://doi.org/10.1021/jo802446y" @default.
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