• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.2801-2805
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• 2010

A nucleophilic substitution reaction of 4-chloro-7-nitrobenzofurazan (NBF-Cl) with anilines in MeOH-MeCN mixtures was conducted at 25, 35, and $45^{\circ}C$. Based on the higher $\beta_{nuc}$ values (1.0 - 1.6) of the reaction and a good correlation of the rate constants with the reduction potentials of the aniline nucleophiles, the present reaction was initiated by a single electron transfer (SET). After this step, the reaction proceeds through a transition state similar to the normal $S_NAr$-Ad.E pathway.

• Bulletin of the Korean Chemical Society
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• v.26 no.2
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• pp.273-277
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• 2005

Dynamic resolution of $\alpha$-bromo tertiary acetamides in asymmetric nucleophilic substitution reaction is described. Intermolecular substitution of $\alpha$-bromo tertiary acetamides with dibenzylamine in the presence of TBAI and $Et_3N$ gave the dipeptide analogues 7-10 with high stereoselectivities up to 90 : 10 dr. Also, cyclic dipeptide analogues 20-29 were produced by the intramolecular nucleophilic cyclization of $\alpha$-bromo tertiary acetamides with low stereoselectivities in 84-42% yields.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.658-661
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• 1991

The gas-phase nucleophilic substitution reaction of pentafluoroanisole with $OH^-$ and ${NH_2}^-$ nucleophiles have been studied theoretically using the AM1 method. Three reaction channels, $S_N2$, IPSO and $S_NAr$ (scheme 1), are all very exothermic so that all are accessible despite the varying central energy barriers which are much lower than the reactants level. In the IPSO and $S_NAr$ channels, the reactants form directly a stable ,${\sigma}$-anion complex which proceeds to form a proton transfer complex via a transition barrier corresponding to a loose ${\pi}$-type complex with the F-(or ${OCH_3}^-$) leaving group. Due to a greater number of probable reaction sites available for $S_NAr$ compared to the other two processes, the $S_NAr$ channel is favored as experimentally observed.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.531-533
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• 1993

• Journal of the Korean Chemical Society
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• v.21 no.6
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• pp.413-421
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• 1977

The orbital mixing analysis was applied to the acid-catalyzed nucleophilic substitution reaction of N-acetylpyrrolidone. It was found that the reactivity of protonated carbonyl carbon is greatly enhanced due to increase in positive charge (for charge controlled reaction) and also increase in LUMO AO coefficient (for orbital controlled reaction) of the carbonyl carbon atom.

• The Korean Journal of Food And Nutrition
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• v.8 no.3
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• pp.172-183
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• 1995

The nucleophilic substitution reactions of p-substituted benzyl bromide with l-substituted N,N-dimethylanilines in methanol and acetonitrile binary solvent mixture which is known to an isodielectric solvent system kinetically and the results are as follows. The positive charge is developed on the reaction center of the substrate and it means that the bond cleavage is preceded more than bond formation in the transition state on the analogy of Hammett px values. The bond form3tlon is not progressed in the case of electron donating substituent of substrate. However, the bond formation is much developed in the case of electron withdrawing substituent of substrate on the analogy of Hammett py values. The nucleophilic attacking ability is shown a highest at 80% (V/V) methanol content and the bond formation is well progressed at the same methanol composition on the result of a cross interaction coefficient, pxy. The result of transition state structure that is applicated to the potential energy surface model is in accord with the result that Is applicated to the reaction susceptibilities. The reaction Is subject to the polarity-polarizability term more than the hydrogen bond donor acidity term by application to the solvatochromic parameter eouation.

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1111-1114
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• 2000

The kinetic study of the enaryloxynitriles via the nucleophilic vinylic substitution reaction of various phenol derivatives with 1-chloro-1-phenyl-2,2-dicyanoethene (1) was conducted in the presence of 1,4-diazabicyclo[2,2,2]octane (DABCO). Nucleo philic vinylic substitution of phenol derivatives with electrophilic olefins carrying sluggish leaving group involves a third-order reaction. The reaction was applied to solution polymerization of diphenol derivatives with p-bis(1-chrolo-2,2-dicyanovinyl)benzene (2), which yielded various polyenaryloxynitriles with moderate molecular weight.

• Journal of the Korean Applied Science and Technology
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• v.6 no.2
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• pp.29-37
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• 1989

Using the quarternary ammonium salts as phase transfer catalyst, the nucleophilic substitution reaction of 1-chlorooctane with sodium-cyanide was investigate kinetically with respect to the formation of octanenitrile. The product was analyzed with gas chromatograph, and quantity of octanenitrile was measured. The reaction condition was considered by the effect of the reaction temperature, of the species and the amount of catalyst, of the speed of strirring, and of the concentration of reactants. The reaction was carried out in the first order on the concentration of 1-chlorooctane and sodium cyanide, respectively. The over-all order was 2nd. The activation energies for the nucleophilic substitution reaction of 1-chlorooctane and 1-bromooctane under tetrabutylammonium hydrogen-sulfate were calculated as 2.05 and 10.08kcal/mol, respectively. The effect of various caltalysts was decreased in the order of tetrabutylammonium bromide, terabutylammonium, tetrabutylammonium hydrogensulfate, and tetrabutylammonium iodide. The reaction rate was dependent on the concentration of sodium-cyanide dissolved in the aqueous phase, and the good result was shown when the mol ratio between 1-chlorooctane and sodium cyanide was one per three.

• Textile Coloration and Finishing
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• v.19 no.4
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• pp.18-25
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• 2007

Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Green 9(G-9) of dinitrothiophene disperse dye were investigated. As soon as G-9 contacted with alkali, instant and continuous decreases of color strength of G-9 followed with increasing time. The hydrolysis rate of G-9 increased with increasing alkali, and it was found that alkali appeared first order dependence. The observed rate constants obtained from hydrolysis of various amount of dye were similar values, and calculation of initial rates showed that G-9 hydrolyzed by first order reaction for dye. Therefore it was confirmed that the overall reaction was second order, $SN_2$ of nucleophilic substitution reaction. Increasing temperature enhanced the hydrolysis of G-9. From the results of hydrolysis performed at various temperatures, it was obtained that activation energy(Ea) was 12.6 kcal/mole, enthalpy of reaction(${\triangle}H$) was 12.0 kcal/mole, and entropy of reaction(${\triangle}S$) was $29.8J/mol{\cdot}K$.

• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.478-481
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• 1985

Nucleophilic substitution reactions between Alkanesulfonylchlorides and p-substituted anilines in methanol-acetonitrile mixture have been studied kinetically. Reactivities of substrates, substituent effects of nucleophile and solvent effects indicate that the studied reaction proceeds via $S_N2$. The kinetic results show that transition state of the reaction between i-PSC and anilines becomes looser as the composition of methanol increases.