• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1749-1753
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reaction of Y-substituted-phenyl picolinates (7a-f) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOK] curves upward while the plot of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ is linear with a positive intercept in all cases. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOK}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ ion and ion-paired EtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The ${\sigma}^{\circ}$ constants result in a much better Hammett correlation than ${\sigma}^-$ constants, indicating that the reaction proceeds through a stepwise mechanism in which departure of the leaving group occurs after the rate-determining step (RDS). $K^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through formation of a cyclic transition state (TS). The catalytic effect decreases as the substituent Y becomes a stronger electron-withdrawing group (EWG). Development of a positive charge on the N atom of the picolinyl moiety through resonance interactions is responsible for the decreasing $K^+$ ion catalysis.

• Textile Coloration and Finishing
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• v.13 no.5
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• pp.24-24
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• 2001

Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N-diacetoxyethyl-2-acylamino-5-ethoxy -2′-bromo-4′,6′-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via S/sub n/2 reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of $OH^{-}$ on the carbon atom, which is in acceptor ring, adjacent to azo group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N,N-diacetoxyethyl group.

• Textile Coloration and Finishing
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• v.13 no.5
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• pp.312-319
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• 2001

Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N- diacetoxyethyl -2- acylamino-5-ethos y -2'-bromo-4',6'-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via $S_N2$ reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of OH- on the carbon atom, which is in acceptor ring, adjacent to auto group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N, N-diacetoxyethyl group.

• Journal of the Korean Chemical Society
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• v.24 no.5
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• pp.347-355
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• 1980

The rate constants for the reaction of ${\alpha}$-naphthalene carbonyl chloride and ${\beta}$-naphthalene carbonyl chloride have been determined in methanol-acetonitrile and methanol-acetone. The rate constant of ${\alpha}$-naphtalene carbonyl chloride is higher than that of ${\beta}$-naphthalene carbonyl chloride. This behavior is consistent with Dewar's number, Nr and also Streitwieser's value ${\sigma}^+$. Since in the transition state carbonyl carbon is transformed to$sp^3$, no peri-hydrogen effect was observed.

• Bulletin of the Korean Chemical Society
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• v.31 no.8
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• pp.2357-2360
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• 2010

Kinetic studies on the pyridinolysis of aryl dithiocyclopentanecarboxyaltes 2 were carried out at $60.0^{\circ}C$ in acetonitrile. In the aminolysis of 2, the $\beta_X$ values were 0.5 - 0.8 with anilines, and there was no breakpoint. However, in the pyridinolysis of 2, biphasic Bronsted plots were obtained, with a change in slope from a large value ($\beta_X{\cong}0.7$) to a small value ($\beta_X{\cong}0.4$) at $pK_{a}^0$ = 5.2. This was attributed to a change in the rate-limiting step from breakdown to the formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in the reaction path, with an increase in the basicity of the pyridine nucleophile. An obvious change in the cross-interaction constant ${\rho}_{XZ}$ from a large positive ($\rho_{XZ}$ = +1.02) value to a small negative value (${\rho}_{XZ}$ = -0.17) supports the proposed mechanistic change.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3811-3816
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• 2013

Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D=0.66-0.99$) with 2, primary normal and secondary inverse ($k_H/k_D=0.78-1.19$) with 4, and primary normal ($k_H/k_D=1.06-1.21$) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transition state, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reaction mechanism, DKIE and activation parameter.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2306-2310
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• 2011

The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 55.0 $^{\circ}C$. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) invariably increase from secondary inverse ($k_H/k_D$ < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.575-579
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• 1991

Reaction of 6${\beta}$-bromopenicillanic acid(4a) with p-nitrobenzylbromide, 3-bromophthalide, chloromethylpivalate and 1-chlorodiethylcarbonate afforded 6${\beta}$-bromopenicillanates(4b~4e). New ${\beta}$-lactam compound, 6-(carboxymethylthio)penicillanic acid(5a) and the other esters(5b~5e) were prepared by nucleophilic substitution reaction of 6${\beta}$-bromopenicillanic acid(4a) and the other esters(4b~4e) with thioglycolic acid.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.561-566
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• 2009

Chloroacylation of 3-amino-2-phenylpyrazole-4-carboxamide (2) using chloroacetyl-(propionyl) chloride affording 6-chloromethyl(ethyl)-1-phenylpyrazolo[3,4-d]pyrimidin-4[5H]-one (3) or (6). Chlorine atom in compound (3) or (6) underwent nucleophilic substitution reaction with primary or secondary amines to give 6-alkyl(aryl)aminomethyl(ethyl)-1-phenylpyrazolo[3,4-d]pyrimidin-4[5H]-one (4a-g,7a-f). When arylaminomethyl( ethyl)pyrazolopyrimidine was treated with formaline (30%) solution in ethanol, underwent Mannich reaction to afford imidazopyrazolopyrimidines (5a-e) and pyrazolopyrimidopyrimidines (8a-e). Chloromethylpyrimidine derivative 3 was converted into the corresponding mercaptomethylpyrazolopyrimidene 9, Which cyclized using bromomalononitrile or phenacyl bromide into pyrazolopyrimidothiazine 11,12.

• Bulletin of the Korean Chemical Society
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• v.16 no.9
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• pp.827-831
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• 1995

Kinetic studies on the reactions of five secondary acylic alkyl arenesulfonates with anilines are carried out in acetonitrile at 65.0 ℃. The magnitude of ρXZ determined (ρXZ=0.12-0.13) is slightly greater than that for the alicyclic series (ρXZ=0.11) under the same experimental condition. Ab initio MO results are found to support the slightly tighter transition state expected from the greater magnitude of ρXZ for the acyclic series. Despite the small variations, the magnitude of ρXZ and the theoretical transition state tightness remain relatively constant for the secondary carbon centers. Secondary kinetic isotope effects involving deuterated aniline nucleophiles show a successively smaller kH/kD(<1.0) value for a more sterically crowded reaction center carbon. This is in accord with the later transition state for bond-making predicted by the Bell-Evans-Polanyi principle for the more endothermic nucleophilic substitution reaction. Further support is provided by the results of the AM1 MO calculations on the reactions of secondary alkyl benzenesulfonates with chloride nucleophile.