• Bulletin of the Korean Chemical Society
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• v.35 no.4
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• pp.1128-1132
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• 2014

A kinetic study on aminolysis of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-i) in MeCN is reported. The Hammett plot for the reactions of 6a-i with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X$ = 1.03 and r = 0.78. The nonlinear Hammett plot is not due to a change in rate-determining step (RDS) but is caused by the resonance stabilization of substrates possessing an electron-donating group in the benzoyl moiety. The Br${\phi}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (6e) with a series of cyclic secondary amines is linear with ${\beta}_{nuc}$ = 0.69, an upper limit for reactions reported to proceed through a concerted mechanism. The aminolysis of 6e in aqueous medium has previously been reported to proceed through a stepwise mechanism with a change in RDS on the basis of a curved Br${\phi}$nsted-type plot. It has been concluded that instability of the zwitterionic tetrahedral intermediate ($T^{\pm}$) in MeCN forces the reaction to proceed through a concerted mechanism. This is further supported by the kinetic result that the amines used in this study are less reactive in MeCN than in $H_2O$, although they are more basic in MeCN over 7 $pK_a$ units.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2403-2407
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• 2009

Second-order rate constants have been measured for two series of nucleophilic displacement reactions, i.e., reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides and those of Y-substituted phenyl benzoates (1a-h) with 4-chlorophenoxide (4-ClPhO–) in 80 mol% $H_2O$/20 mol% DMSO at 25.0 ${\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot for reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.72. Reactions of 1a-h with 4-chlorophenoxide result in also a linear Br$\phi$nsted-type plot with ${\beta}_{lg}$ = –0.62, a typical ${\beta}_{lg}$ value for a concerted mechanism. The Hammett plots correlated with ${\sigma}^o\;and\;{\sigma}^-$ constants show many scattered points for reactions of 1a-h with 4-chlorophenoxide. In contrast, the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with $\rho_Y$ = 2.26 and r = 0.53, indicating that expulsion of the leaving group occurs at the rate-determining step (RDS) either in a concerted mechanism or in a stepwise pathway. However, a stepwise mechanism with leaving group departure being the RDS is excluded since the leaving Y-substituted phenoxide is less basic and a better nucleofuge than the incoming 4-ClPh$O^-$. Thus, the reactions have been concluded to proceed through a concerted mechanism, in which bond formation between the nucleophile and electrophilic center is more advanced than expulsion of the leaving group in the transition state on the basis of the magnitude of ${\beta}_{nuc}\;and\;{\beta}_{lg}$ values.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.214-218
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• 2009

Second-order rate constants ($k_N$) have been measured for nucleophilic substitution reactions of S-4-nitrophenyl thiobenzoate with a series of alicyclic secondary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Br$\phi$nsted-type plot exhibits a downward curvature, i.e., $\beta_{nuc}$ decreases from 0.94 to 0.34 as the amine basicity increases. The reactions in the aqueous DMSO have also been suggested to proceed through a zwitterionic tetrahedral intermediate (T${\pm}$) with change in the RDS on the basis of the curved Br$\phi$nsted-type plot. The reactions in the aqueous DMSO exhibit larger $k_N$ values than those in the aqueous EtOH. The macroscopic rate constants ($k_N$) for the reactions in the two solvent systems have been dissected into the microscopic rate constants ($k_1\;and\;k_2/k_{-1}$ ratio) to investigate effect of medium on reactivity in the microscopic level. It has been found that the $k_2/k_{-1}$ ratios are similar for the reactions in the two solvent systems, while $k_1$ values are larger for the reactions in 20 mol % DMSO than for those in 44 wt % EtOH, indicating that the larger $k_1$ is mainly responsible for the larger $k_N$. It has been suggested that the transition state is more stabilized in 20 mol % DMSO through mutual polarizability interaction than in 44 wt % EtOH through H-bonding interaction.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2785-2788
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• 2009

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2393-2397
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• 2009

Second-order rate constants ($k_{HOO}$‒) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted phenyl benzenesulfonates (1a-g) with $HOO^-$ ion in $H_2O$ at $25.0\;{\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot is linear with ${\beta}_{lg}$ = ‒0.73. The Hammett plot correlated with with ${\sigma}^-$ constants results in much better linearity than ${\sigma}^o$ constants, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS) either in a stepwise mechanism or in a concerted pathway. However, a stepwise mechanism in which departure of the leaving group occurs in the RDS has been excluded since $HOO^-$ ion is more basic and a poorer leaving group than the leaving Y-substituted phenoxide ions. Thus, the reactions of 1a-g with $HOO^-$ ion have been concluded to proceed through a concerted mechanism. The $\alpha$-nucleophile $HOO^-$ ion is more reactive than its reference nucleophile $OH^-$ ion although the former is ca. 4 p$K_a$ units less basic than the latter (i.e., the $\alpha$-effect). TS stabilization through intramolecular H-bonding interaction has been suggested to be irresponsible for the $\alpha$-effect shown by $HOO^-$ ion, since the magnitude of the $\alpha$-effect is independent of the electronic nature of substituent Y in the leaving group. GS destabilization through desolvation of $HOO^-$ ion has been concluded to be responsible for the $\alpha$-effect found in the this study.

• Bulletin of the Korean Chemical Society
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• v.31 no.1
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• pp.75-81
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• 2010

The reaction of N,N-diethyl carbamates of 1H-[1,2,3]triazolo[4,5-b]pyridin-1-ol (4-HOAt) 7, 3H-[1,2,3]triazolo[4,5-b]pyridin-3-ol (7-HOAt) 8, 1H-benzo[d][1,2,3]triazol-1-ol (HOBt) 9, 6-chloro-1H-benzo[d][1,2,3]triazol-1-ol (Cl-HOBt) 10, 6-(trifluoromethyl)-1H-benzo[d][1,2,3]triazol-1-ol ($CF_3$-HOBt) 11, and 6-nitro-1H-benzo[d][1,2,3]triazol-1-ol ($NO_2$-HOBt) 12 with morpholine and piperidine in $CH_3CN$ underwent acyl nucleophilic substitution to give the corresponding carboxamide derivatives. The reactants and products were identified by elemental analysis, IR and NMR. We measured the kinetics of these reactions spectrophotometrically in $CH_3CN$ at a range of temperatures. The rates of morpholinolysis and piperidinolysis were found to fit the Hammett equation and correlated with $\sigma$-Hammett values. The values were 1.44 - 1.21 for morpholinolysis and 1.95 - 1.72 for piperidinolysis depending on the temperature. The $Br{\phi}$nsted-type plot was linear with a $\beta_lg = -0.49 \pm 0.02$ and $-0.67 \pm 0.03$. The kinetic data and structure-reactivity relationships indicate that the reaction of 9-12 with amines proceeds by a concerted mechanism. The deviation from linearity of the correlation ${\Delta}H^#$ vs. ${\Delta}S^#$ and plot of $logk_{pip}$ vs. $logk_{morph}$ and $Br{\phi}$nsted-type correlation indicate that the reactions of amines with carbamates 7 and 8 is attributed to the electronic nature of their leaving groups.

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2909-2912
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• 2009

The amines studied in this study are less reactive toward ethyl propiolate (3) in MeCN than in H$_2$O although they are 7 to 9 pK$_a$ units more basic in the aprotic solvent. The reactivity of morpholine and deuterated morpholine toward 3 is found to be identical, indicating that proton transfer occurs after rate-determining step (RDS). The fact that kinetic isotope effect is absent excludes a stepwise mechanism in which proton transfer occurs in RDS as well as a concerted mechanism in which nucleophilic attack and proton transfer occur concertedly through a 4-membered cyclic transition state (TS). Thus, the reactions have been concluded to proceed through a stepwise mechanism in which proton transfer occurs after RDS. Brønsted-type plots are linear with small ${\beta}_{nuc}$ values, i.e., ${\beta}_{nuc}$ = 0.29 in H$_2$O and ${\beta}_{nuc}$ = 0.51 in MeCN, indicating that bond formation is not advanced significantly in RDS. The small ${\beta}_{nuc}$ value also supports the conclusion drawn from the study of kinetic isotope effect.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.93-97
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-2-methylbenzoates (5a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Hammett plots for the aminolysis of 5a-e are nonlinear, e.g., substrates possessing an electron-donating group (EDG) in the benzoyl moiety deviate negatively from the linear line composed of substrates bearing no EDG. In contrast, the Yukawa-Tsuno plots for the same reactions exhibit excellent linear correlations with ${\rho}_X$ = 0.30-0.59 and r = 0.90-1.15, indicating that the nonlinear Hammett plots are caused by stabilization of the substrates possessing an EDG through resonance interactions but are not due to a change in the rate-determining step (RDS). The Br${\phi}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.66-0.82. Thus, the aminolysis of 5a-e has been suggested to proceed through a stepwise mechanism in which departure of the leaving group occurs at the RDS. The ${\rho}_X$ and ${\beta}_{nuc}$ values for the aminolysis of 5a-e increase as the reactivity of the substrates and amines increases, indicating that the reactivity-selectivity principle is not applicable to the current reactions.