• Bulletin of the Korean Chemical Society
• /
• 제22권4호
• /
• pp.395-400
• /
• 2001

The effects of ortho- (R = H and CH3) and Y-substituents (Y = OCH3, CH3H and CN), which are directly attached to the carbonyl carbon, on the protonation equilibria of the para-X-substituted benzoyl derivatives, 4-X -2, 6-di-R-C6H2-C(=O)-Y, are investigated theoretically using the B3LYP method with 6-31+G* basis set. Structurally, both of the (B) and (BH+ ) forms in the species with R = H are nearly coplanar regardless of the Y-substituents implying that the steric repulsion between Y-substituent and R = H is relatively small. In the species with R = CH3 , the tortional angle (Θ) between the carbonyl moiety and aryl ring varies from zero to near right angle depending on the degree of steric repulsion between Y and R = CH3 and the resonance demand. However the reaction energies, ΔG°, for the protonation processes are more favorable for R = CH3 than for R = H due to stronger electron donating effect of R = CH3 , although the species with R = CH3 are unfavorable sterically. On the other hand, the Hammett type plots are progressively better correlated with б+ than with б values on going from Y = OCH3 to Y = CN for both species with R = H and CH3 indicating that the degree of resonance delocalization between carbonyl moiety and X-substituent is increased for a more electron accepting Y-substituent. Nevertheless the effects of R = CH3 on the magnitude of Hammett type reaction constants ( б or б+ ) are not much different from those of R = H.

• Bulletin of the Korean Chemical Society
• /
• 제34권7호
• /
• pp.2111-2116
• /
• 2013

This paper reports substituent effects on the conformational changes in polyaniline (PAni) derivatives. PAni, poly-o-toluidine (POT), and poly-o-anisidine (POA) were formed by potentiodynamic electropolymerization in aqueous solution containing (+)-camphorsulfonic acid (CSA) as a dopant. UV-Vis spectroscopy and cyclic voltammetry measurements revealed that the methyl group showed a greater steric hindrance than the methoxy group. Further, the doping level decreased with increasing steric hindrance. The sign pattern of the circular dichroism (CD) bands for POA was opposite to that for PAni. However, no CD bands were observed in POT. The steric hindrance caused helical inversion, but at a high level of steric hindrance, the helical conformation could not be adopted, because of the reduced doping level. The reduced crystallinity was greatly affected by the decreased doping level. The steric effect influenced the polymer conformation and the doping level, thus determining the optical activity, morphology, and crystallinity of the PAni derivatives.

• Bulletin of the Korean Chemical Society
• /
• 제6권2호
• /
• pp.99-102
• /
• 1985

Substituent effects of substrate and nucleophile for the reaction of substituted phenacyl tosylates with pyridines were determined conductometrically in acetonitrile. Activation parameters for these reactions were also calculated. The substituent effects in nucleophile were increased with electron-donating power of pyridines and Br${\o}$nsted linear relationship was shown. Rate constant was increased by both electron-donating and electron-attracting groups in the substrate. It seems that dissociative S$_{N}$2 ("loose" transition state) mechanism is operating in the case of electron-donating substituents while associative S$_{N}$2 ("tight" transition state) mechanism is operative in the case of electron-attracting substituents.

• Bulletin of the Korean Chemical Society
• /
• 제15권6호
• /
• pp.453-455
• /
• 1994

Semiempirical MO calculations are applied to estimate the substituent effects on acylations of the nonfused N-vinyl-2-amino $\beta-lactams$ having frameworks analogous to 3-cephems. The stabilization energy for the reaction intermediate of the nucleophilic attack by the hydroxide ion is selected as the reactivity index and calculated by AM1 and PM3 methods for the model $\beta-lactams$ with substituents at the C1 and N-vinyl terminal positions. The reactivities are larger for -SH connected to the C1 and strong $\pi-acceptors$ at the N-vinyl terminal implying the large reactivity for known active cephalosporins. Quantum chemical calculation of stabilization energy could be useful in correlating antibiotic activities of many compounds obtained as derivatives of a lead compound.

• Bulletin of the Korean Chemical Society
• /
• 제20권10호
• /
• pp.1172-1176
• /
• 1999

Nucleophilic substitution reaction of Y-benzyl bromide with X-pyridines are investigated in DMSO at 45.0℃. Biphasic rate dependence is observed on varying the substituents in the substrate (Y) as well as in the nucleophile (X). The two well-defined straight lines in the Hammett (ρy) and Bronsted ( βx) plots are interpreted to indicate the changes in transition-state structure, a decrease in bond cleavage as the substituent on the substrate is changed from electron-donors ( ρy < 0) to electron-acceptors ( ρy > 0), and an increase in the extent of bond formation with the corresponding changes of the substituent on the pyridine. A Jencks' type analysis of separate polar (ρ) and resonance (ρr) effects can also be accounted for by the change of the transition-state structure, not by the variable combination of polar and resonance effects.

• Bulletin of the Korean Chemical Society
• /
• 제16권7호
• /
• pp.604-609
• /
• 1995

The relative dissociation constants of 4-substituted bicyclo[2,2,2]octane-1-carboxylic acids, 4-substituted quinuclidines, and 3-and 4-substituted pyridines were collected from a number of sources. In order to understand the actual substituent effects with a combination of inductive effect (σI) and resonance effect (σR) components. The DSP correlation has been employed statistically for each of the p-and m-series. The inductive effect from the m-position was 1.2 times more effective than that from the p-position and the requirement of σR+ for the best-fit led to the conclusion that pyridine system belongs to the σ+-class reactivity. Also compared with results from Yukawa-Tsuno's LArSR treatment and relevant treatment.

• 한국염색가공학회지
• /
• 제33권4호
• /
• pp.169-181
• /
• 2021

Five dyes based on phthalocyanine, a dye on azo, and a dye on anhraquinone were prepared from corresponding starting material to investigate the effects of substituent on thermal-stability of dyes which is essentially required to apply to the color filters. Synthesized dyes were confirmed their chemical structure using by 1H-NMR, MASS and Elemental analysis. The thermal-stability was evaluated by the weight reductions measured by TGA analysis comparing to that of conventional C.I. Pigment Blue 15:6. The absorption maxima were measured by UV-VIS spectrophotometer then the effects of substituent on absorption maximum was also investigated.

• Bulletin of the Korean Chemical Society
• /
• 제23권5호
• /
• pp.758-760
• /
• 2002

• Bulletin of the Korean Chemical Society
• /
• 제19권9호
• /
• pp.1000-1002
• /
• 1998

• Bulletin of the Korean Chemical Society
• /
• 제10권5호
• /
• pp.481-481
• /
• 1989