• Bulletin of the Korean Chemical Society
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• v.7 no.3
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• pp.186-190
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• 1986

Effects of substituents in the nucleophile(X), the substrate(Y) and the leaving group(Z) on the structure of $S_N2$ transition states have been analyzed by considering effects of four components, electrostatic($E_{es}$), exchange repulsion ($E_{ex}$), polarization($E)_{pl}$) and charge transfer($E_{ct}$) terms, of interaction between the reactants on the degree of bond making and bond breaking. Prediction of net effects of all substituents(X, Y and Z) on the degree of bond making were found to be clearcut whereas the effect of an electron withdrawing group on the substrate (Y = EWG) on the degree of bond breaking was complex; the substituent(Y = EWG) is normally carbon-leaving group($C^{\ast}$-L) bond tightening($E_{pl}$ dominance) but becomes $C^{\ast}$-L bond loosening when the bond is strongly antibonding ($E_{ct}$ dominance). Our model calculations on the reaction of $CH_2XNH_2$ with $YCH_2COOCH_2Z$ using energy decomposition scheme have confirmed that predictions based on our analysis are correct.

• Journal of the Korean Chemical Society
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• v.9 no.3
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• pp.148-151
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• 1965

Kinetics of reactions of chloride and bromide ions with benzyl chloride and bromide have been investigated in 90% ethanol solution. Semi-quantitative analysis of the results shows that the bond-formation is more important than the bond-breaking and furthermore in bond-formation the energy gain due to bond-formation is less than the increase in electron affinity of the nucleophile.

• Journal of the Korean Chemical Society
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• v.32 no.4
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• pp.301-310
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• 1988

Reaction rates for mononuclear heterocyclic rearrangement of N-(5-phenyl-1,2,4-oxadiazol-3-yl)-N'-arylformamidines into 3-acylamino-1-aryl-1,2,4-triazoles were determined spectrophotometrically in dioxane/water (50 : 50, v/v). There are two different reaction paths according to pH. One is pH-independent path, the other is pH-dependent one. In pH-independent path, the result of substituent effect by IYT equation show that N-H bond breaking as well as new N-N bond formation controls the reaction rate. In pH-dependent path, concave-upward Hammett plot was observed. It can be concluded that new N-N bond formation is more advanced than N-H bond breaking in transition state for electron-donating substituents, but N-H bond breaking is more advanced than new N-N bond formation for electron-withdrawing substituents.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.857-860
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• 1994

We have calculated the ${\pi}$-electron density, atom self-polarizability, and free valence on each atom of N-(2-chlorobenzyl)-pyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-2-chloropyridinium salts using a simple Huckel method in order to discuss their intramolecular photocyclization reaction in a qualitative method. Our calculation qualitatively predicts that photocyclization occurs through forming radicals as a reaction intermediate by breaking a C-Cl bond after photoexcitation into a triplet state via intersystem crossing from an initially excited singlet state. We noticed that this C-Cl bond breaking is aided by ${\pi}$-complex formation between a chlorine atom and the ${\pi}$ -electrons of the neighboring ring in the triplet state and a stronger ${\pi}$-complex bond makes C-Cl bond breaking, i.e., radical formation, much easier. A chlorine atom will form a stronger ${\pi}$ -complex bond to a benzyl ring of N-(benzyl)-2-chloropyridinium than a pyridinium ring of N-(2-chlorobenzyl)-pyridinium because the former can donate its ${\pi}$-electron more easily than the latter. The chlorine at position 15 of N-(2-chlorobenzyl)-2-chloropyridinium salt in the excited state also provides its ${\pi}$-electron to the benzyl ring. So this ${\pi}$-electron can increase the bond strength of the $\pi-complex.$ Therefore, the strength of ${\pi}$-complex follows the order of N-(2-chlorobenzyl)-2-chloropyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-pyridinium salts and thus the radical formation rate. This provides us with an intramolecular photocyclization reaction rate of the same order as given above.

• Journal of the Korean Chemical Society
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• v.19 no.2
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• pp.116-122
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• 1975

Determination has been made of the kinetics of the reaction of benzyl arenesulfonates with pyridine in acetone. The substituent effects of the leaving groups in benzyl arenesulfonates are correlated by Hammett equations, with the exception of p-MeO and $p-NO_2$ groups, where the electron attracting substituents in the benzyl arenesulfonate increase the rate. The substituent effects of the leaving groups are as expected due to the nucleophilic attack of amine on the benzyl carbon atom. This can be understood in terms of changes in bond formation (C-N) and bond breaking (C-O) in the transition state with charges in electron-attracting ability of the substituents. The predicted substituent effects may indicate a small increase in bond formation and thus a tighter transition state, in benzyl p-bromobenzene sulfonate than in benzyl p-nitrobenzenesulfonate. Predicting made by Thornton concerning the substituent effects on $S_N2$ transition state structures agrees with the changes in bond formation and bond breaking.

• Bulletin of the Korean Chemical Society
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• v.6 no.3
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• pp.162-164
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• 1985

Nucleophilic substitution reaction of dansyl chloride with anilines in various solvents have been investigated. The Bronsted ${\beta}$ and Hammett ${\rho}_N$ values indicated that the bond formation is advanced more than the bond breaking at the transition state. Solvatochromic correlations also predicted the importance of bond formation at the TS, showing a greater contribution of polarity (${\pi}^{\ast}$) compared to hydrogen bond donor acidity (${\alpha}$). The effect of solvent on rate was found to violate the reactivity-selectivity principle.

• Journal of the Korean Chemical Society
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• v.19 no.1
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• pp.11-15
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• 1975

Kinetic study of halogen exchange for N,N-dimethylcarbamoyl chloride and N,N-diethylcarbamoyl chloride in acetone by using radioisotopic halide ions has been carried out at two temperatures as a part of studying the reactivity of carbonyl carbon atom. The order of nucleophilicity showed a similar tendency as that for alkyl chloroformate, but reaction rate is much slower than that for solvolysis and alkyl chloroformate. The activation parameters,${\Delta}H^*$and${\Delta}S^*$ were found to decrease in sequence $Cl^{\rightarrow}Br^{\rightarrow}I^-$ for N,N-dialkylcarbamoyl chlorides. The results are interpreted in terms of solvation effect, degree of bond-breaking and bond-formation and electronic requirements.

• Journal of the Korean Chemical Society
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• v.17 no.6
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• pp.406-410
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• 1973

Kinetic study of halide exchange for dimethylsulfamoyl chloride in dry acetone by using radioisotopic halide ions has been carried out at two temperatures. The result of the order of nucleophilicity, as compared with benzenesulfonyl chloride, shows a similar tendency but reaction rate is slower, more than $10^{-2}$times, than benzenesulfonyl chloride. The activation parameter, ${\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$ decrease in sequence $Cl^-\;>\;Br^-\;>\;I^-$ in dimethylsulfamoyl chloride but it is the reverse order found for benzenesulfonyl chloride. The results are interpreted with bond-breaking, bond-formation, and electronic requirments, and in the light of HSAB Principle.

• Journal of the Korean Chemical Society
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• v.36 no.3
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• pp.366-375
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• 1992

The aminolysis of carbamates are studied MO theoretically using AM1 method. The results indicated that the reactivity is determined by bond-making and-breaking and steric effects; as a result the $B_{AC}2$ mechanism is favored due to favorable contribution of bond formation in agreement with experimental results. We found that although thermal 2＋2 reaction is forbidden, it becomes allowed when the total electrons involved are six in a four-center reaction and proceeds by a consecutive onestep mechanism. Comparison of activation barriers show that greater energy is required in breaking a sigma bond compared with the energy required for breaking a $\pi$ bond, by 17 kcal/mol and the six membered ring structure is favored about 5 kcal/mol sterically.

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.211-213
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• 1991

The ground state of the oxygen molecule is calculated by various methods of coupled cluster approaches and many body perturbation theory using a double zeta plus polarization basis set and the UHF reference state. All the methods employed are capable of describing the oxygen molecule near the equilibrium bond length and the separated atom, but do not correctly depict the breaking of the multiple bond. For this basis set, including more correlations does not necessarily improve the agreement with experiment for molecular properties such as bond lengths and dissociation energies.