• Bulletin of the Korean Chemical Society
• /
• v.30 no.7
• /
• pp.1481-1484
• /
• 2009

When isolated phenol or a small phenol-solvent cluster is excited to the $S_1\;state\;of\;{\pi}{\pi}^*$ character, the hydrogen atom of the hydroxyl group dissociates via a ${\pi}{\sigma}^*$ state that is repulsive along the O-H bond. We computationally investigated the substitution effects of an amino group on the excited state hydrogen transfer reaction of phenol. The time-dependent density functional theory (TDDFT) with B3LYP functional was employed to calculate the potential energy profiles of the ${\pi}{\pi}^*$ and the ${\pi}{\sigma}^*$ excited states along the O-H coordinate, together with the orbital shape at each point, as the position of the substituent was varied. It was found that the amino substitution has an effect of lowering the ${\pi}{\sigma}^*$ state and enhancing the excited state hydrogen transfer reaction.

• Journal of the Korean Ceramic Society
• /
• v.37 no.8
• /
• pp.787-791
• /
• 2000

Samples with the nominal composition, Bi2-xGexSr2CaCu2O8＋$\delta$ (x=0, 0.1, 0.2, 0.3, 0.4, 0.5) were prepared by the solid-state reaction method. We have studied the effect of substitution Ge for Bi and investigated the superconducting properties by changing oxygen content with Ge substitution. It was found that temperature difference, ΔK, between TCon and TCzero was considerably smaller in the samples prepared by the intermediate pressing method than that in the samples by the solid-state reaction method. We found the solubility limit of Ge to the 80 K single phase was around x=0.3. Within the solubility limit, lattice constant c decreased with the increase of x. In the region of the 80K single phase, the onset critical temperature TCon increased and excess oxygen content decreased with increase of x.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.6
• /
• pp.1785-1788
• /
• 2010

• Bulletin of the Korean Chemical Society
• /
• v.8 no.5
• /
• pp.424-425
• /
• 1987

Alkylation and allylation of arylborates give mono(ipso) and/or di(ortho and ipso) substitution products. Those factors which promote polarization or ionization of alkylating agents favor di substitution. The ${\sigma}$-type(ipso) substitution reaction of arylborates involves direct interaction of the carbon-boron bonds rather than predissociation of arylborates into aryllithiums and boranes.

• Journal of Korean Society for Atmospheric Environment
• /
• v.14 no.1
• /
• pp.25-33
• /
• 1998

We have studied the reduction of NO by propane over perovskite-type oxides prepared by malic acid method. The catalysts were modified to enhance the activity by substitution by substitution of metal into A or B site of perovskite oxides. In addition, the reaction conditions, such as temperature, $O_2$ concentration, space velocity have been studed. In the $LaCoO_3$ type catalyst, the partial substitution of Ba, Sr into A site enhanced the catalytic activity in the reduction of NO. In the $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3(x=0 \sim 1.9)$ catalyst, the partial substitution of Fe into B site enhanced the conversion of NO, but excess amount of Fe decreased the conversion of NO. The surface area and catalytic activity of perovskite catalysts prepared by malic acid method showed higher values than those of solid reaction method. In the $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3$ catalyst, the conversion of NO increased with increasing $O_2$ concentration and contact time. The introduction of water into reactant feed decreased the catalytic activity.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.10
• /
• pp.2801-2805
• /
• 2010

A nucleophilic substitution reaction of 4-chloro-7-nitrobenzofurazan (NBF-Cl) with anilines in MeOH-MeCN mixtures was conducted at 25, 35, and $45^{\circ}C$. Based on the higher $\beta_{nuc}$ values (1.0 - 1.6) of the reaction and a good correlation of the rate constants with the reduction potentials of the aniline nucleophiles, the present reaction was initiated by a single electron transfer (SET). After this step, the reaction proceeds through a transition state similar to the normal $S_NAr$-Ad.E pathway.

• Journal of the Korean Chemical Society
• /
• v.31 no.6
• /
• pp.534-541
• /
• 1987

The study of reaction mechanism for the substitution of ethylenediamine (en) for Cl and Hedta from $[CoCl(Hedta)]^-$ in the presence of $Hg^{2+}$ ion was carried out by uv and CD spectra. From the kinetic data, we proposed that the first ethylenediamine be substituted through the associative reaction path by means of interaction of $Hg^{2+}$ ion with Co(III), and that the second and the third ethylenediamine be substituted stepwise. From the optical purities of $[Co(en)_3]^{3+}$ which was formed after reaction, we suggested the critical stereochemical step and new substitution reaction paths.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.9
• /
• pp.1208-1254
• /
• 2002

Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl) acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.1
• /
• pp.104-106
• /
• 1989

Halopyrimidines such as 2-chloro-, 5-bromo, and 4,6-dichloro-5-nitropyrimidine undergo substitution reactions with superoxide anion radical (superoxide) to give the corresponding hydroxypyrimidines under suitable conditions. Parallel experiments employing hydroxide instead of superoxide strongly indicate that the reactivity of superoxide is comparable to that of the hydroxide in the reaction with halopyrimidines. The results seem to provide a piece of information in favor of the nucleophilic substitution rather than electron-transfer mechanism in the title reaction.

• Bulletin of the Korean Chemical Society
• /
• v.6 no.3
• /
• pp.162-164
• /
• 1985

Nucleophilic substitution reaction of dansyl chloride with anilines in various solvents have been investigated. The Bronsted ${\beta}$ and Hammett ${\rho}_N$ values indicated that the bond formation is advanced more than the bond breaking at the transition state. Solvatochromic correlations also predicted the importance of bond formation at the TS, showing a greater contribution of polarity (${\pi}^{\ast}$) compared to hydrogen bond donor acidity (${\alpha}$). The effect of solvent on rate was found to violate the reactivity-selectivity principle.