Pseudo-first-order rate constants (kobsd) have been measured for reactions of phenyl Y-substituted-phenyl carbonates with alkali metal ethoxides (EtOM, M = Li, Na, and K). The plot of kobsd vs. [EtOM] curves upward for the reaction of diphenyl carbonate with EtOM but is linear for that with EtOK in the presence of 18-crown-6-ether (18C6), indicating that the reaction is catalyzed by M+ ions and the catalytic effect disappears in the presence of 18C6. The kobsd values for the reactions with EtOK have been dissected into kEtO and kEtOK, i.e., the second-order rate constants for the reactions with dissociated EtO− and ion-paired EtOK, respectively. The Hammett plots correlated with σ− and σ constants exhibit highly scattered points, while the Yukawa–Tsuno plots result in an excellent linear correlation with ρ = 2.11 and r = 0.21 for kEtO -, and ρ = 1.62 and r = 0.26 for kEtOK, implying that the reaction proceeds through a concerted mechanism. The catalytic effect (i.e., the kEtOK/kEtO - ratio) is independent of the electronic nature of the substituent Y. Thus, it has been concluded that K+ ion catalyzes the reaction by increasing the electrophilicity of the reaction center.

Pseudo-first-order rate constants (k obsd ) have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol at 25.0 ± 0.1 o C. The plot of k obsd vs.[EtOM] is linear for the reaction of 9 with EtOK. However, the plot curves downwardly for those with EtOLi and EtONa while it curves upwardly for the one with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of k obsd into k EtO _ and k EtOM (i.e., the second-order rate constant for the reaction with dissociated EtO -and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order indicating that the reaction is inhibited by Li+ and Na + ions but is catalyzed by 18C6-crowned K + ion. The reactivity order found for the reactions of 9 contrasts to that reported previously for the corresponding reactions of 1, i.e.,, indicating that the effect of changing the electrophilic center from P=O to P=S on the role of M + ions is significant. A four-membered cyclic transition-state has been proposed to account for the M + ion effects found in this study, e.g., the polarizable sulfur atom of the P=S bond in 9 interacts strongly with the soft 18C6-crowned K + ion while it interacts weakly with the hard Li + and Na + ions.