• Journal of the Korean Chemical Society
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• v.33 no.5
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• pp.468-476
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• 1989

Kineties for the reactions of pyridines with 1-anthracenesulfonyl chloride (1-ASC) and 3-phenanthrenesulfonyl chloride (3-PSC) was investigated in methanol as solvent. Structural variation in pyridine followed $Br{\o}$ nsted and Hammett relations for both 1-ASC and 3-PSC; the corresponding coefficients, {\beta}\;and\;{\rho}\;at\;20^{\circ}C$ were 0.55, -3.5 for 1-ASC, and 0.43, -2.6 for 3-PSC respectively. Reactivity-selectivity principle was checked in competition system 1-ASC/3-PSC. As a result, this principle was found to hold at experimental temperatures, whereas to break down over in the range of isoselective temperature ($34.3^{\circ}C$). Judging from the above results and activation parameters, we concluded that these reactions proceeded by synchronous $S_n2$ mechanism in rate-determining step.

• Journal of the Korean Chemical Society
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• v.29 no.1
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• pp.15-22
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• 1985

Kinetic studies of nucleophilic substitution reaction of substituted benzoyl cyanides and benzoyl chlorides with pyridines were conducted at 25$^{\circ}C$ in pure acetone solvent. Results showed that (ⅰ) magnitudes of $_{\rho}_S$, $_{\rho}_N$ and ${\beta}$ associated with a change of substituent in the nucleophile indicate relatively advanced bond-formation in the transition state, (ⅱ) the potential energy surface model is able to predict the reaction mechanism, but it is unable to predict the transition state variation to a more product-like transition state, where bond-formation is much more progressed than bond breaking, upon changing the leaving group to that with better leaving ability (ⅲ) the quantum mechanical model predicted the product-like transition state and slightly better leaving ability of CN- as compared with Cl-.

• Journal of the Korean Chemical Society
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• v.43 no.4
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• pp.456-460
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• 1999

Rates of 1-adamantyl fluoroformate with substituted pyridines ($3-CH_3,\;4-CH_3,\;H,\;3-Cl,\;3,4-(CH_3)_2,\;3,5-(CH_3)_2$) in methanol have been measured by conductometric method at various temperatures and concentrations. The activation parameters (${\Delta}H^{\neq},\;{\Delta}S^{\neq}$) and Hammett reaction constant (${\rho}$) or Bronsted coefficient (${\beta}$) were evaluated from rate constants. The activation entropies are large and negative, and the activation enthalpies are small and positive. The Hammett reaction constant (${\rho}$) and Bronsted coefficient (${\beta}$) values were -4.15 and 0.63, respectively. From the above results, it may be concluded that this reaction proceeds to a concerted displacement mechanism in methanol.

• Journal of the Korean Chemical Society
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• v.21 no.1
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• pp.38-43
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• 1977

The rate constant of the reaction of 3-or 4-substituted pyridines with benzyl benzenesulfonate in acetone at $35^{\circ}C$ were determined by an electric conductivity method. According to the Hammett plot, the rates were increased the electron donating ability at the $S_N2$ reaction of benzyl benzenesulfonate with pyridine and 4-$NH_2$ pyridine was correlated with ${\sigma}^+$ than Hammett ${\sigma}$ value. This result was explained that $NH_2$ group and N atom in pyridine are largely contribute by resonance. In Br$\"{o}$nsted plot, 4-amino and electron attracting group were deviated from the increasing part at linearity. It was considered to solvent effects on substituents. A mechanistic possibility was proposed to account for the results. Some activation parameters were also calculated.

• Korean Journal of Food Science and Technology
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• v.32 no.2
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• pp.238-245
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• 2000

This study was investigated to compare the changes of flavors in sesame oil with roasting temperature $(110^{\circ}C{\sim}230^{\circ}C)$. In the results of analyzing the volatile flavor compounds of sesame oil with GC and GC/MS, 26 pyrazines, 11 pyridines, 9 thiazoles, 6 furans, 8 pyrroles, 5 phenols, 8 aldehydes, 8 hydrocarbons, 7 alcohols, 2 indoles, 3 ketones, 10 acids, 4 nitriles, 7 esters, and 5 others were isolated, identified, and quantified. The total amount of flavor compounds was increased with roasting temperature. Detected flavors could be devided into top(peak No. $1{\sim}91$), middle$(92{\sim}197)$ and last note$(198{\sim}224)$ by rentention time. The top notes(initial content 19.87 ppm) which contain pyrazines and provide representative roasted flavors were increased significantly with roasting temperature. Initial content of middle note(17.72 ppm) was increased to 36.71 ppm at $170^{\circ}C$, to 95.61 ppm at $220^{\circ}C$, and to 138.62 ppm at $230^{\circ}C$. Last note was almost unchanged up to $170^{\circ}C$ and increased at $190^{\circ}C$, whereas it indicated a tendency to decrease at $230^{\circ}C$. Pyrazines such as methylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine which indicate the major components among volatile flavors were increased slightly up to $150^{\circ}C$ and revealed the higher increase than any other components above $170^{\circ}C$. This tendency was also similar to pyridines, thiazoles, and furans. Most of these compounds are assumed to be developed by thermochemical reactions of sesame components by roasting above $170^{\circ}C$. It seemed that a lot of increase in phenols above $210^{\circ}C$ resulted from the production of guaiacol. Acids were almost unchanged up to $190^{\circ}C$, increased at $210^{\circ}C$, and then decreased above $220^{\circ}C$. It seemed to be resulted from pyrolysis of free fatty acids formed from thermal oxidation of oil.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1042-1046
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• 2012

The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of diethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit the two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with rate-limiting expulsion of the isothiocyanate leaving group from a trigonal bipyramidal pentacoordinated intermediate. The relatively large ${\beta}_x$ values with more basic and less basic pyridines imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb.

• Preventive Nutrition and Food Science
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• v.13 no.1
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• pp.12-17
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• 2008

Douchi, a popular seasoning agent in Chinese dishes prepared by the Aspergillus oryzae fermentation of black beans, was subjected to supercritical fluid extraction (SFE) and gas chromatography-mass spectrometry analysis for its volatile components. A total of 73 components were identified in two commercial brands, which were positively confirmed and quantified. Among the common components in the two brands were 18 acids, 12 alcohols, 11 aldehydes, 9 esters, 1 furan, 11 other oxygen-containing compounds, 4 pyrazines, 2 pyridines and 5 miscellaneous compounds. The most abundant components found were acetic acid, benzoic acid, 2,6-dimethylpyrazine, 2-piperidinone, 3-methylbutanoic acid, maltol, 4-ethylphenol, 2-methylpropanoic acid, butanoic acid, 2-pyrrolidinone, all fatty acids and some esters.

• Journal of the Korean Chemical Society
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• v.25 no.4
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• pp.263-269
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• 1981

The substituted pyridinium salts of oxochloromolybdates(V) have been prepared characterized by visible and infrared spectra, and magnetic moments. The electrical conductance of aqueous solutions of substituted pyridinium salts have been measured over a range of concentrations. The results indicate that the complex anions are monomeric in the solid. The magnetic moments of the complexes are similar to the spin-only values. Substituted pyridines are present as pyridinium cation in solid state.

• 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.

• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.715-720
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• 2002

Kinetic studies of the reaction of Z-aryl cyclobutanecarboxylates with X-pyridines in acetonitrile at $55.0^{\circ}C$ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterion ic tetrahedral intermediate, T $\pm$ . These mechanistic conclusions are drawn based on (i) the large magnitude of ${\rho}X$ and $\rhoZ$, (ⅱ) the positive sign of ${\rho}XZ$ and the larger magnitude of $\rhoXZ$ than normal SN2 processes, (ⅲ) a small positive enthalpy of activation, ${\Delta}H{\neq}$, and a large negative, ${\Delta}S{\neq}$, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.