• Bulletin of the Korean Chemical Society
• /
• v.28 no.8
• /
• pp.1353-1357
• /
• 2007

Second-order rate constants (kN) have been determined spectrophotometrically for reactions of Y-substituted phenyl 2-furoates (1a-h) with piperidine and morpholine in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 oC. The Brønsted-type plot exhibits a downward curvature for the reactions with strongly basic piperidine but is linear for the reactions with weakly basic morpholine. The slope of the curved Brønsted-type plot changes from -1.25 to ?0.28 as the pKa of the conjugate acid of the leaving aryloxides decreases. The pKa at the center of the Brønsted curvature, defined as pKa°, was determined to be 6.4. The aminolysis of 1a-h has been concluded to proceed through a stepwise mechanism on the basis of the curved Brønsted-type plot. The reactions of Ysubstituted phenyl cinnamates (2a-g) with piperidine resulted in a curved Brønsted-type plot with a pKa° values of 6.4. However, the curved Brønsted-type plot has been suggested to be not due to a change in the RDS but due to a normal Hammond effect of a concerted mechanism, since the Brønsted-type plot for the corresponding reactions with morpholine results in also a curved Brønsted-type plot with a pKa° values of 6.1. The furoates with a basic leaving group (i.e., 1b-g) are less reactive than the corresponding cinnamates (i.e., 2b-g). The k2/ k-1 ratios for the reactions of 1b-h are much smaller than unity, which has been suggested to be responsible for their low reactivity.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.7
• /
• pp.1359-1363
• /
• 2008

Second-order rate constants have been determined spectrophotometrically for reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature, i.e., the slope decreases from 0.74 to 0.34 as the amine basicity increases. The $pK_a$ at the center of the Brønsted curvature, defined as $pK_a^o$, has been determined to be 9.1. Comparison of the Brønsted-type plot for the reactions of 2 with that for the corresponding reactions of 2,4-dinitrophenyl 2-furoate (1) suggests that reactions of 1 and 2 proceed through a common mechanism, although 2 is less reactive than 1. The curved Brønsted-type plot has been interpreted as a change in RDS of a stepwise mechanism. The replacement of the O atom in the furoyl ring by an S atom (1 $\rightarrow$ 2) does not alter the reaction mechanism but causes a decrease in reactivity. Dissection of the apparent second-order rate constants into the microscopic rate constants has revealed that the $k_2/k_{-1}$ ratio is not influenced upon changing the nonleaving group from furoyl to thiophenecarbonyl. However, $k_1$ has been calculated to be smaller for the reactions of 2 than for the corresponding reactions of 1, indicating that the C=O bond in the thiophenecarboxylate 2 is less electrophilic than that in the furoate 1. The smaller k1 for the reactions of 2 is fully responsible for the fact that 2 is less reactive than 1.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.4
• /
• pp.767-771
• /
• 2008

Second-order rate constants have been measured spectrophotometrically for the Michael-type reaction of 1-(Xsubstituted phenyl)-2-propyn-1-ones (2a-f) with amines in $H_2O$ at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. A linear Brønsted-type plot is obtained with ${\beta}_{nuc}$ = 0.25 ${\pm}$ 0.02, a typical $\beta_{nuc}$ value for reactions which proceed through a stepwise mechanism with attack of amine on the electrophilic center being the rate-determining step. Secondary alicyclic amines are found to be more reactive than isobasic primary amines. The Hammett plot for the reactions of 2a-f with morpholine is not linear, i.e., the substrate with a strong electron-donating group (e.g., 4-MeO) exhibits a negative deviation from the Hammett plot. However, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.62 and r = 0.82. Thus, it has been proposed that the nonlinear Hammett plot is not due to a change in the ra te-determining step but due to ground-state stabilization through resonance interactions.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.8
• /
• pp.1459-1463
• /
• 2008

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.3
• /
• pp.575-579
• /
• 2008

• Bulletin of the Korean Chemical Society
• /
• v.29 no.12
• /
• pp.2509-2512
• /
• 2008

• Bulletin of the Korean Chemical Society
• /
• v.29 no.3
• /
• pp.580-584
• /
• 2008

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of Y-substituted phenyl benzoates (1a-h) with azide ion (N3) in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the azidolysis exhibits a downward curvature, i.e., the slope (b lg) changes from 0.97 to 0.20 as the basicity of the leaving group decreases. The pKao (defined as the pKa at the center of the Brnsted curvature) is 4.8, which is practically identical to the pKa of the conjugate acid of N3 ion (4.73). Hammett plots correlated with s o and s constants exhibit highly scattered points for the azidolysis. On the contrary, the corresponding Yukawa-Tsuno plot results in an excellent linear correlation with r = 2.45 and r = 0.40, indicating that the leaving group departs in the rate-determining step. The curved Brnsted-type plot has been interpreted as a change in the rate-determining step in a stepwise mechanism. The microscopic rate constants (k1 and k2/k1 ratio) have been calculated for the azidolysis and found to be consistent with the proposed mechanism.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.3
• /
• pp.585-589
• /
• 2008

Second-order rate constants (kN) have been measured for reactions of Y-substituted phenyl 2-thiophenecarboxylates (6a-h) with morpholine and piperidine in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the reactions of 6a-h with morpholine is linear with b lg = 1.29, indicating that the reactions proceed through a tetrahedral zwitterionic intermediate (T?). On the other hand, the Brnsted-type plot for the reactions of 6a-h with piperidine exhibits a downward curvature, implying that a change in the rate-determining step occurs on changing the substituent Y in the leaving group. Dissection of kN into microscopic rate constants (i.e., k1 and k2/k1 ratio) has revealed that k1 is smaller for the reactions of 6a-h than for those of Y-substituted phenyl 2-furoates (5a-h), while the k2/k1 ratio is almost the same for the reactions of 5a-h and 6a-h. It is also reported that modification of the nonleaving group from the furoyl (5a-h) to the thiophenecarbonyl (6a-h) does not influence pKao (defined as the pKa at the center of the Brnsted curvature) as well as the k2/k1 ratio.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.3
• /
• pp.381-384
• /
• 2002

Second-order-rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a) with a series of secondary alicyclic amines in H2O containing 20 mole % DMSO at 25.0 $^{\circ}C$ . The ester 1a is less reactive than 4-nitrophenyl 2-furoate (1b) but more reactive than 4-nitrophenyl benzoate (1c) except towards piperazinium ion. The Brønsted-type plots for the aminolyses of 1a, 1b and 1c are linear with a $\beta$nuc value of 0.92, 0.84 and 0.85, respectively, indicating that the replacement of the CH=CH group by a sulfur or an oxygen atom in the benzoyl moiety of 1c does not cause any mechanism change. The reaction of piperidine with a series of substituted phenyl 2-thiophenecarboxylates gives a linear Hammett plot with a large $\rho^-$ value ($\rho^-$ = 3.11) when $\sigma^- $ constants are used. The linear Brønsted and Hammett plots with large $\beta$nuc and $\rho^-$ values suggest that the aminolysis of 1a proceeds via rate-determining break-down of the addition intermediate to the products.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.4
• /
• pp.772-776
• /
• 2008

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 3,4-dintrophenyl 2-furoate (2) with a series of secondary alicyclic amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide (DMSO) at 25.0 ${^{\circ}C}$. The Bronsted-type plot exhibits a downward curvature for the aminolysis of 2, which is similar to that reported for the corresponding reactions of 2,4-dintrophenyl 2-furoate (1). Substrate 2 is less reactive than 1 toward all the amines studied but the reactivity difference becomes smaller as the amine basicity increases. Dissection of the second-order rate constants into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but slightly larger $k_1$ value than that of 1. Steric hindrance has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1, since the ortho-substituent of 1 would inhibit the attack of amines (i.e., the $k_1$ process).