• Journal of Integrative Natural Science
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• v.7 no.4
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• pp.266-272
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• 2014

Oxocane high explosives substituted to explosive group such as azide (-CH2N3), nitrate (-CH2ONO2), and hydrazine (-CH2N2H3) are investigated theoretically the acid catalyzed reaction using the semiempirical MINDO/3, MNDO and AM1 methods to use as the guidelines of high explosives. The nucleophilicity and basicity of oxocane high explosives can be explained by the value of negative charge on oxygen atom of oxocane and the reactivity in propagation step can be represented by the value of positive charge on carbon atom and low electrophile LUMO energy. It was known that carbenium ion was favorable due to the stable energy (11.745~25.461 Kcal/mol) between oxonium ion and carbenium ion in the process of cyclic oxonium ion of oxocane high explosives being converted to open carbenium ion in oxocane high explosives. The value of concentration of cyclic oxonium ion and open carbenium ion in equilibrium status was found to be a major determinant of mechanism, it was expected to react faster in the prepolymer propagation step in SN1 mechanism than in that of SN2.

• 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.

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.835-839
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• 2010

The rate constants of solvolyses of 2,2,2-trichloro-1,1-dimethylethyl chloroformate ($\underline{I}$) in 33 solvents can be well correlated using the extended Grunwald-Winstein equation, with incorporation of the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivities towards changes in the scale having values of $1.42\;{\pm}\;0.09$ for l and $0.39\;{\pm}\;0.05$ for m, respectively. The activation enthalpies are ${\Delta}H^{\neq}\;=\;12.3$ to $14.5\;kcal{\cdot}mol^{-1}$ and the activation entropies are -28.2 to $-35.5\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$, consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.14 in MeOH/MeOD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4117-4121
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• 2012

The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.10-18
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• 1990

Solvolyses of p-substituted benzyl bromides have been studied in dimethylsulfoxide-water and N,N-dimethylformamide-water mixtures by kinetic method. To determine the ionizing power, Y and the nucleophilicity, $N_{BS}$, the solvolyses of 1-adamantyl halides, t-butyl halides, and methyl tosylate in the same solvent mixtures have been investigated. The solvatochromic parameters for each dimethylsulfoxide-water mixtures have been determined by substituting into the Taft's linear solvatochromic energy relationships with measured $ν_{max}$. The solvolyses of p-substituted benzyl bromides have been found to proceed by borderline mechanism in which bond formation is more advanced than bond cleavage in the transition state based on the m, l values and ${\beta},{\rho}_s$, values.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.2 no.1
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• pp.17-21
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• 2016

Alkali metal fluoride sources (MFs) such as potassium fluoride (KF) have been widely used as a fluoride source in the nucleophilic displacement reaction. However, they have low solubility and nucleophilicity in most of the organic solvents. Bulky fluoride sources such as tetrabutylammonium fluoride (TBAF) were substituted for MFs to improve these properties. However, hygroscopic property of TBAF makes it less convenient for handling as well as its strong basic property can make the side-reaction occur. Recently, novel fluoride sources have been developed to solve these problems. In this paper, we would like to introduce coordinated fluoride sources as a new fluoride sources such as tetrabutylammonium tetra(t-butyl alcohol)-coordinated fluoride, crown ether metal complex fluoride, and various bulky alcohols coordinated fluoride complexes. In particular, bulky alcohol coordinated fluoride source could generated by the controlled hydrogen-bonded of fluoride with alcohols and these fluoride sources have better stability and reactivity with showing low hygroscopic property. The study of these fluoride sources will help to understand the characteristic of [$^{18}F$]fluoride for increasing the radiochemical yield in the [$^{18}F$]radiofluorination.

• Bulletin of the Korean Chemical Society
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• v.11 no.1
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• pp.49-54
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• 1990

The gas-phase thermolysis reactions of ${\alpha}$- and ${\beta}$-methylated ethyl formates, Y = $CH-X-CHR_1CH_2R_2$ where X = Y = O or S and $R_1\;=\;R_2$ = H or $CH_3$, are investigated theoretically using the AM1 method. The experimental reactivity order is reproduced correctly by AM1 in all cases. The thermolysis proceeds through a six-membered cyclic transition state conforming to a retro-ene reaction, which can be conveniently interpreted using the frontier orbital theory of three-species interactions. The methyl group substituted at $C_{\alpha}\;or\;C_{\beta}$ is shown to elevate the ${\pi}$-HOMO of the donor fragment (Y = C) and depress the ${\sigma}^{\ast}$-LUMO of the acceptor fragment ($C_{\beta}$-H), increasing the nucleophilicity of Y toward ${\beta}$-hydrogen which in turn increases the reactivity. The two bond breaking processes of the $C_{\alpha}$-X and $C_{\beta}$-H bonds are concerted but not synchronous so that the reaction takes place in two stages as Taylor suggested. The initial cleavage of $C_{\alpha}$-X is of little importance but the subsequent scission of $C_{\beta}$-H occurs in a rate determining stage.

• Bulletin of the Korean Chemical Society
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• v.15 no.6
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• pp.473-477
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• 1994

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates $(1,\;X-C_6H_4SO_2-OC_6H_4-Y)$ with aryloxides $(Z-C_6H_4O^{-})$ and ethoxide $(EtO^-)$ in absolute ethanol at $25^{circ}C$. The nucleophilicity of aryloxides increases with increasing electron donating ability of the substituent (Z) on aryloxides, and results in a good Hammett correlation with $\sigma^{-}$ constant. The reactivity of 1 toward aryloxides and ethoxide shows also significant dependence on the electronic nature of the substituent X and Y. Large positive ${\sigma}_{acyl}$ values have been obtained for the reaction of 1 with phenoxide and ethoxide, indicating that the leaving group departure is little advanced at the transition-state of the rate-determining step. This has been further supported from the fact that ${\sigma}^-$ constant gives extremely poor Hammett correlation, while ${\sigma}^0$ does reasonably good correlation for the reaction of 1 with ethoxide. Thus, the present sulfonyl-transfer reaction is proposed to proceed via a ratedetermining attack of nucleophile to the sulfur atom of 1 followed by a fast leaving group departure.

• Bulletin of the Korean Chemical Society
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• v.17 no.11
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• pp.1056-1061
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• 1996

Solvolysis rates of 1-(4-methoxyphenyl)-l-phenyl-2,2,2-trifiuoroethyl chloride (1) and 1-(4-methoxyphenyl)-1-phenylethyl chloride (2) were measured in a variety of aqueous binary solvents, and the solvent effect was treated with the Grunwald-Winstein equation. The solvent effect on the solvolysis of 1 failed to give a single linear correlations using the ordinary Y or YCl, but exhibited the wide split pattern which could not be related to the solvent nucleophilicity. The improved correlations with YBnCl and extended dual-parameter treatment, log (k/k0)=mYCl+hI (mΔYΔ), were observed for the solvolysis of 1. These results suggest that the incipient cationic charge in the solvolysis of 1 is delocalized strongly into the aryl-rings in the transition state. While the solvent effect on the solvolysis of 2 is better correlated with Y or YCl than YBnCl but the linearity is not satisfactory. The correlation is comparably improved by the use of the extended Grunwald-Winstein equation, log (k/k0)=0.81YCl+0.26NOTs (R=0.994, SD=±0.12), indicating the cationic charge of reaction center of 2 was localized mostly in the transition state.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.4 no.2
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• pp.51-56
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• 2018

Azeotropic drying process is routinely applied to enhance nucleophilicity of $[^{18}F]$fluoride ion during the nucleophilic production of PET radiotracers; however, the drying process requires usually 15-25 min. Due to the high demand of employing fluorine-18 ($t_{1/2}=109.8min$) in PET radiopharmaceutical production, several research groups have focused on the method development, obviating tedious removal process of the residual target water ($[^{18}O]H_2O$) for $[^{18}F]$fluoride ion complex to be used in radiofluorination. Some development in radiofluorination in a mixed organic solvent system was demonstrated with various aliphatic substrates, but only kryptand as a phase transfer agent was utilized in the reported method. Here, we extend to investigate the development scope of applicability with basic alkyl ammonium salt as a phase transfer agent through the extensive elution efficiency study and radiofluorination outcome for aliphatic radiofluorination.