• Journal of the Korean Chemical Society
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• v.47 no.2
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• pp.96-103
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• 2003

Density Functional Theory(DFT) calculations are performed to estimate the hydrogen bonding interaction energies in pyridine-water and amino-substituted pyridine-water complexes. Some equilibrium properties are also obtained for these complexes at B3LYP/aug-cc-pVDZ level. It is shown that the amino substitution increases the proton affinity of pyridine and stabilizes the hydrogen bond. The degree of stabilization upon formation of the complex varies with the number and the position of the amino groups.

• Korean Chemical Engineering Research
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• v.50 no.3
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• pp.417-420
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• 2012

This study is about reduction reaction making 2, 4-dinitrotoluene (2, 4-DNT) to 2, 4-toluene diisocyanate (2,4-TDI) with Pd/$SiO_2$. Catalytic systems based on Pd/$SiO_2$ at about $200^{\circ}C$ and under 100 bars of carbon monoxide. We studied the effect of pyridine on the yield of the TDI. TDI was not created without pyridine, but created with pyridine, at the reaction result. According to research, homogeneous synthesis of TDI with direct carbonylation, palladium and pyridine complexion is known to catalyze. When adding pyridine the reason of TDI synthesis is palladium leaching, ICP-AES was performed to confirm it. As a result, the proportion of Pd loaded in $SiO_2$ was decreased 52% than before, after the reaction by adding 20 vol% pyridine. Generating TDI by adding pyridine might be the effect of the complex ion, which is composed of leached palladium and pyridine.

• Journal of the Korean Chemical Society
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• v.44 no.3
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• pp.184-189
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• 2000

ab initio molecular orbitaI calculation is performed to estimate the substituent effects for meta-substituted pyridines. Electrostatic potentials are obtained from ab initio wavefunctions of the optimized structures for the meta-substituted pyridines. Electrostatic potenhals are shown to be minimum at nitrogen atom of pyridines. The potenttial minima are good correlated with the substituent constants, ${\sigma}_m$ and with the ${\Delta}pK_a$, respectively. It is found that the electrostatic potential minima can be used as a useful measure of substituent effects.

• Proceedings of the Membrane Society of Korea Conference
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• 1997.10a
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• pp.131-132
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• 1997

1. 서론 : 이온 복합막은 투과증발을 통한 유기수용액의 탈수에 있어서 높은 수투과유량과 선택도를 나타내는 것으로 알려져 있다. 그러나 장시간 운전시에 이온 복합막은 막표면에 있는 금속 counterion이 feed에 씻겨버리기 때문에 분리능의 급격한 감소를 띠게 된다. counterion이 유기물일 경우에는 막속으로 확산되어 우기농축물에 포함될 문제가 있다. counterion이 고분자이면, 막 효능의 안정성이 증가되지만 막 제조과정이 다소 어려워진다. 아크릴산과 스티렐폰산을 포함하고 있는 개질 PAN막을 이용한 피리딘 수용액의 탈수에 관한 이전의 연구에서, 피드내의 피리딘과 막내의 산 기능기 사이에 형성된 in-situ complex가 막의 투과물사이에 특별한 반응이 없거나 막과 주요 투과 물간에 수소결합이 있는 막보다 더 좋은 탈수 효능을 나타냄이 확인되었다. 본 연구에서는 포스페이트를 함유하고 있는 폴리아크릴로니트릴 막의 제조와 피리딘 수용액의 탈수 효능에 대해 언급할 것이다.

• Journal of the Korean Chemical Society
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• v.43 no.4
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• pp.378-383
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• 1999

Ab initio calculation is performed to estimate the substituent effects for Para-substituted pyridines. Electrostatic potentials are obtained from ab initio molecular orbital wavefunctions of optimized structures for substituted pyridines. Electrostatic potentials are computed to be minimum at nitrogen atom of pyridines. The potential minima are good correlated with the substituent constants, ${\sigma}_p$ and with the ${\Delta}pKa$. It is shown that the electrostatic potential minima can be used as a measure of substituent effects.

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.280-286
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• 1987

The effect of substituent inleaving group on the rates of reactions of phenacyl substituted-benzenesulfonates with pyridine was determined conductometrically in acetonitrile and in methanol at 35, 45, and $55^{\circ}C$, respectively. The reaction rate became faster in proportion to electron-attracting ability of substituent, which indicates that the substituent in leaving group can directly control reaction rate. It was shown that the specific to the carbonyl carbon as the rate-determining step.

• Journal of the Korean Chemical Society
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• v.25 no.2
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• pp.110-118
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• 1981

Kinetics and mechanism for the reaction of substituted phenacyl bromides with substituted pyridines have been determined at 25, 35 and $45^{\circ}C$ in methanol and dimethylformamide by the conductivity method. The rate constants for the reaction of various pyridines with phenacyl bromide shown that electron-donating substituents in the pyridine increase the rate, while electron-attracting one decrease in both solvents. The effect of substituents in substrate, the rate being increased by electron-attracting substituents. This is as expected for nucleophilic attack of amines on the carbon atom. Isokinetic and $Br{\psi}nsted$ linear relationship were shown in the reaction of phenacyl bromide with pyridines in both solvent in which isokinetic temperature were obtained 614, $202^{\circ}K$ and ${\beta}$ values were 0.29, 0.36 in methanol and dimethylformamide respectively. In the case of the reaction of substituted phenacyl bromide with pyridines, isokinetic temperature decreases with increasing electron-attracting ability of the substituents in the phenacyl bromide, while the ${\beta}$ values were reverse. From the above results, it can be inferred that N…C bond formation decreases progressively from p-chloro- to p-methoxyphenacyl bromide and the bond formation predominates in DMF than methanol. The ${\rho}$ values of Hammett equation of the reaction of phenacyl bromide with substituted pyridines are negative in both solvent, but its value was larger negative in DMF than methanol and the ${\rho}$ value of that of substitutted substrates with pyridine was 0.3, the low value is ascribed to direct $S_N2$ attack of the nitrogen atom in pyridine ring at the methylene carbon.

• Journal of the Korean Chemical Society
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• v.26 no.6
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• pp.383-388
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• 1982

$Mo_2O_4Cl_2$$(X-py)_4{\cdot}2H_2$O and $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O have been prepared. The infrared, electronic and reflectance spectra, molar conductances and magnetic susceptibility data of complexes are reported. $Mo_2O_4Cl_2$$(X-py)_4{\cdot}2H_2$O (X-py were 3-and 4-cyanopyridine, nicotinamide, 3,5-lutidine and 2-amino-4-picoline) were obtained by hydrolysis of the corresponding substituted pyridinium oxopentachloromolybdates(Ⅴ). Addition of water and substituted pyridines to molybdenum(Ⅴ)-thiocyanate ethylacetate extract yielded brown compounds, $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O where X-py were pyridine, ${\alpha}$, 3-bromopyridine 3,5-lutidine, 3-benzoylpyridine and 4-acetylpyridine. Binuclear, $Mo_2O_4Cl_2(X-py)_4{\cdot}2H_2$ prepared from hydrolysis of $(X-pyH)_2[MoOCl_5]{\cdot}H_2O$ were diamagnetic and nonelectrolytes. The anion of $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O was formulated as dimer and electrolyte.

• Journal of the Korean Chemical Society
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• v.23 no.4
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• pp.243-247
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• 1979

Kinetics of the reaction of phenethyltosylate with substituted pyridines at 50, 60 and 70$^{\circ}C$ in acetonitrile were investigated by an electric conductivity method. The effects of substituents on the reaction of phenethyltosylate with pyridines were discussed. The rates of reaction were increased with electron donating power of substituents of pyridines. The isokinetic relationship was shown $E_{\alpha}$ and ${\Delta}S^{\neq}$, it's temperature was 240$^{\circ}$K. Bronsted plots were excellent linear except for 4-amino pyridine given by the following equation, logk=O. 22pKa-3.71 (r=O. 986). According to a plot of log k against Hammett substituent constants, the Iinearity was good except for bamino pyridine too, log k= -1.330${\sigma}$+0.08 (r= -0.987). In both cases, deviation of 4-amino pyridine from linearity was considered to solvent effect, resonance effect and ${\sigma}$ value itself. From all the above results, this reaction was found typical $S_N2$ reaction which the rates of reaction was determined by C…N bond formation at transition state.

• Korean Journal of Optics and Photonics
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• v.1 no.2
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• pp.142-148
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• 1990

Surface-enhanced Raman scattering (SERS) experiment of pyridine (CsHsN) has been performed at silverpyridine interface by use of long range surface plasmon (LRSP) which is generated in the Sarid-type attenuated total reflection (A TR) structure consisting of prism. dielectric. metal and dielectric media. Generation of LRSP has ben confirmed by observing the propagation of the LRSP. Raman signal of pyridine adsorbed on a silver surface in the above layered structure has been observed and compared with the bulk Raman signal and SERS signal from the chemically adsorbed pyridine. SERS experiment by use of LRSP has not yet reported to the best of our knowledge.wledge.