• Bulletin of the Korean Chemical Society
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• v.17 no.7
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• pp.604-607
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• 1996

Semiempirical PM3 MO calculations are applied to estimate both 1-atom (X=S,O,C) and 3-substituent (Y=R, CH2R, SR, CH2SR) effects on the reactions of some 1-atom-replaced and 3-substituted cephem-like β-lactam compounds of thiacephems, oxacephems, and carbacephems. Stabilization energy (SE) of the reaction intermediate for the reaction with a hydroxyl ion can be used to evaluate the facility of a reaction and selected as a chemical reactivity index. With the 1-atom effect only, the SE values obtained imply that thiacephems are generally more reactive than the other two cephem-like molecules and the reactivity order is thiacephems>oxacephems>carbacephems. When it comes to the 3-substituent (Y=R, CH2R, SR, CH2SR) effect, chemical reactivity can be best realized by using a 3-substituted thiacephem molecule capable of giving a resonance-stabilized and electron-rich leaving group after the reaction with a nucleophile. SE values, however, decrease in most cases when an additional intervening ethylene group is present (Y=CH2R, CH2SR). The overall 3-substituent reactivity tendency is SR>CH2SR>R>CH2R.

• Journal of the Korean Chemical Society
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• v.19 no.4
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• pp.240-245
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• 1975

Substituent effects of benzyl substrates for the reaction of substituted benzyl(Z) arenesulfonate(X) with dimethylanilines in (Y) acetone at $35^{circ}$ were studied. The interactions between Z and Y disappeared when changed from electron withdrawing group to releasing group in benzyl substrates. The disappearance of interactions between Z and Y infers change of mechanism from $S_N2 to S_N1$ in substituent Z.

• Journal of the Korean Chemical Society
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• v.26 no.3
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• pp.142-147
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• 1982

Substituent effects on the fluorescence of 2-(substituted anilino) nicotinic acids and their aluminum chelate compounds were examined, and satisfactory linear relationships between Hammett substituent constant, ${\sigma}$, and the lowest excited singlet energy levels were obtained. Effects of solvent on the native and aluminum chelate compounds were also investigated.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1754-1758
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• 2014

The nucleophilic substitution reactions of bis(Y-aryl) chlorothiophosphates (1) with X-pyridines are investigated kinetically in acetonitrile at $35.0^{\circ}C$. The free energy relationships with both X and Y are biphasic concave upwards with a break point at X = 3-Ph and Y = H, respectively. The sign of cross-interaction constants (CICs; ${\rho}_{XY}$) is positive with all X and Y. Proposed mechanism is a stepwise process with a rate-limiting leaving group departure from the intermediate with all X and Y. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). In the case of Y = electron-withdrawing groups, the cross-interaction between Y and Y, due to additional substituent Y, is significant enough to change the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1, indicative of the change of mechanism from a rate-limiting bond formation to bond breaking.

• Archives of Pharmacal Research
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• v.4 no.2
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• pp.91-98
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• 1981

The substituent effects on the fluorescence of 2-(substituted anilino)benzoic acids and their aluminum chelate compounds were examined and satisfactory linear relationships between Hammett substitute constants, .sigma. and the lowest excited singlet energy levels were obtained. But fluorescence intensity only made a qualitative relationship with .sigma. values of substituent groups. Effects of solvents and metal ions on the native and metal chelate fluorescence of the above derivatives were also investigated.

• Archives of Pharmacal Research
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• v.23 no.6
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• pp.579-584
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• 2000

To explore the effect of substituents' on phenyl motif on sulfonyl function of novel anticancer 4-phenyl-1-benzenesulfonylimidazolidinones (1), electron donating or withdrawing sub-stituents were introduced at 3 or 4-position and the analogs were tested against human lung (A549) and colon (HCT-15) cancer cell lines. Quantitative structure activity relation-ship of the 4-substituted series shows that only STERIMOL L values are well correlated. The increment of substituent's volume enhances the activity against both cell lines. The small substituent at 3-position additionally increases the activity. However naphthyl group in place of phenyl reduces the activity, Therefore the phenyl motif with sterically large substituent at 4-position and small substituent at 3-position may be important for their activity. Integration of these substituents' effects into the structural design led to discover the more potent analog, 4-phenyl-1-(N-acetylindoline-5-sulfonyl) imidazolidinone (1n).

• Journal of the Korean Chemical Society
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• v.68 no.4
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• pp.185-190
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• 2024

Recently, it was reported that the benzobisoxazole (BBO) molecule can be used for independent modulation of the HOMO and LUMO energy levels. In this study, we utilized this interesting property of BBO to quantitatively investigate the substituent effects according the substituents. We designed and proposed four BBO model systems (1BBO, 2BBO, 3BBO and 4BBO) by extending the π-conjugation lengths based on a BBO molecule. Two directions of substitution (x-axis and y-axis) and 15 various substituents were considered. From strong correlation between the LUMO energy levels of x-axis substitution and HOMO energy levels of y-axis substitution calculated from DFT method, it is found that the standardization of substitution effects can be established from BBO model systems. In addition, we demonstrated that the HOMO values of y-axis substituted 3BBO show the best performance to define the order of substituent effects. Our proposed way can be used to expect the substituent effect of any arbitrary substituents and develop the organic sensors and organic light emitting diodes.

• Bulletin of the Korean Chemical Society
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• v.21 no.12
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• pp.1202-1206
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• 2000

Transmission of substituent effects through 5-membered heteroaromatic rings is investigated theoretically at the RHF/6-31+G and B3LYP/6-31+G levels using the equilibria for the $OH^- addition to five-membered heteroaromatic aldehydes (5MHA). The transmission efficiency (S) in 5MHA(A) increases in the order NH>O>S>PH but the order exactly reverses in 5MHA($T^-$). This is originated by the delocalizability of the ${\pi}$ lonepair on Y, $$n_\pi$(Y)$. A better correlation is obtained with ${\sigma}_p^-$ in the Hammett plots with positive slope, $p_z$ > 0, indicating that the substituent (Z) effects are not transmitted by a direct conjugation. The magnitude of $p_z$ for Y=NH is the largest among the heteroaromatic systems, which is consistent with the largest transmission efficiency change $({\Delta}S)$. The equilibria for the addition processes are favorable in the gas phase $({\Delta}G^o<0)$, which reverses to unfavorable in aqueous solution $({\Delta}G^o>0)$ due to the relatively large salvation energy of $OH^-$ in the initial state in aqueous solution. The orders of ${\Delta}G^o$ and $p_z$ in the gas phase are almost maintained in solution.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.262-266
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• 2002

Computations are presented for the ortho- and para-substituted benzyl alcohol-$H_2O$ clusters. A variety of conformers are predicted, and their relative energies are compared. Binding energies of the clusters are computed, and detailed analysis is presented on the effects of substitution on the strength of the hydrogen bond in the clusters. F- and $NH_2-$ substituted clusters are studied to analyze the effects of electron-withdrawing and electron-pushing groups. In para-substituted clusters, the inductive effects are dominant, affecting the binding energies in opposite way depending on whether the hydroxyl group is proton-donating or -accepting. For ortho-substituted clusters, more direct involvement of the substituting group and the resulting geometry change of the hydrogen bond should be invoked to elucidate complicated pattern of the binding energy of the clusters.

• 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.