• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.625-631
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• 1993

The types of the products of the reactions between RuH(NO)(Cyttp) and alkynes are sensitive to the nature of alkynes. Terminal, nonactivated alkynes (HC${\equiv}$CR, R=Ph, hexyl and $CH_2OH)$ produce acetylide complexes and terminal (HC${\equiv}$CR, R=C(O)Me, COOEt) or internal activated ones (RC${\equiv}$ CR, R=COOMe) lead to form alkenyl complexes. On the other hand, internal nonactivated alkynes (RC${\equiv}$CR, R=Ph) do not show reactivity toward RuH(NO)(Cyttp). These products can be rationalized by the cis-concerted mechanism but the radical pathway appears to work in the reaction of propargyl chloride. From the spectroscopic data, the trigonal bipyramidal structure with a linear NO group is proposed for these products.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.636-642
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• 1992

Preferential solvation (PS) phenomena of solutes based on solvent polarity, $E_T$ and AN, were studied by UV/vis. and NMR spectra in MeOH binary mixtures. According to the extent of solvent-solvent interaction, different solvation phenomena were found. PS concept was applied to explain the reactivity of tert-butyl halides solvolysis. The findings of solvation phenomena have been related to the rate of solvolysis and PS suggested as a reason for the solvent dependence of the rates of reaction. Moreover, we found that the results of principal components analysis using six parameters are in good accordance with the results of PS phenomena in mixed methanol systems.

• Bulletin of the Korean Chemical Society
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• v.17 no.7
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• pp.653-655
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• 1996

A comparative molecular field analysis (CoMFA) was carried out for the correlation of the transition state structures and the reaction rates for the SN2 reaction of 4-nitrophenyl benzoate and its sulfur analogs with anionic nucleophiles. The CoMFA analysis showed that both steric and electrostatic effects are important, and the steric contribution increased when nucleophiles are alkoxides or arylsulfides. In this study, we have demonstrated that the CoMFA analysis can be expanded beyond the scope of dealing with reactants and products. The reactant complex and transition state conformations generated along the reaction path can be more appropriately used for the correlation of structures and reaction rates.

• Bulletin of the Korean Chemical Society
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• v.15 no.8
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• pp.654-658
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of p-and m-nitrophenyl 2-furoates (4 and 5, respectively) with alkali metal ethoxides ($EtO^-M^+$) in absolute ethanol at 25$^{\circ}$C. The reactivity of $EtO^-M^+$ toward 4 is in the order $EtO^-K^+$ > $EtO^-Na^+$> $EtO^-Li^+$ > $EtO^-K^+$+ 18-crown-6 ether. This is further confirmed by an ion pairing treatment method. The present result indicates that (1) ion paired $EtO^-M^+$ is more reactive than dissociated $EtO^-$ ; (2) the alkali metal ions ($K^+,\;Na^+,\;Li^+$) behave as a catalyst; (3) the catalytic effect increases with increasing the size of the metal ion. A similar result has been obtained for the reaction of 5, however, the catalytic effects shown by the metal ions are more significant in the reaction of 5 than in that of 4.

• Bulletin of the Korean Chemical Society
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• v.5 no.5
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• pp.179-182
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• 1984

MINDO/3 theoretical studies were carried out on sigmatropic hydrogen rearrangements in systems with central nitrogen atom; three systems studied being (1) N-methylformaldimine, (2) nitrous acid, and (3) formaldoxime-nitrosomethane systems. It was found that in system (1), 1,3-H shift is preferred whereas in systems (2) and (3), 1,2-H shifts are favored. The relative order of reactivity for the three systems was found to be (2) < (3) < (1), which is exactly the opposite to that found for the corresponding systems with central carbon atom.

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.183-187
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• 1993

Aryl carbenic anion radicals have been generated from the corresponding alkoxy-aryl diazo compounds by unimolecular decomposition reaction in various electrolyte/solvent systems. The electrochemical reductions of alkoxy-aryl diazo compounds in the electrolyte/solvent system are shown to initially be a one-electron process which affords the corresponding anion radicals. The unimolecular loss of nitrogen is favored at the propagation step and accelerated by the oxygen and carbon atoms of alkoxy group adjacent to the diazo function. The structure of the carbene anion radical in the termination is considered to be a resonance hybrid.

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.193-196
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• 1987

The gas phase pyrolyses of eight esters have been studied by MNDO-MO method. In the ethylformate pyrolysis, ${\alpha}$-methylation had a steric releasing effect whereas ${\beta}$-methylation had a steric crowding in the transition state; the latter, however, is over-compensated by a greater electronic repulsion resulting in a net steric releasing effect. Considerations of formal charges and geometrical changes involved in the activation led us to propose a pyrolysis mechanism in which a preequilibrium of acidic proton transfer is followed by the rate-limiting bond polarization of $C_{\alpha}$-O bond in a cyclic transition state.

• Bulletin of the Korean Chemical Society
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• v.17 no.2
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• pp.201-205
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• 1996

The crystal and molecular structure of thiourea dioxide, (NH2)2CSO2, was determined by x-ray single crystal diffraction techniques. Lattice constants are a=10.669(2), b=10.119(2), and c=3.9151(5) Å with the space group Pnma and Z=4. The thiourea portion of the molecule has a planar conformation. When the two oxygen atoms are included, the sulfur atom is at the apex of a trigonal pyramid formed with the two oxygen atoms and the carbon atom as the base. The crystal structure is stabilized by strong intermolecular hydrogen bonds. Ab initio calculations were performed to investigate the bonding features and reactivity of thiourea dioxide. The calculated bond order of S-C is only 0.481. The hydrogen bond energy was computed to be 22.3 kcal/mol for dimer. MEP analysis reveals that the sites on nucleophilic reactions are S and C atoms.

• Bulletin of the Korean Chemical Society
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• v.11 no.3
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• pp.241-244
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• 1990

The photochemistry of 1-Methyl-2-cyclohexenyl aryl ketones (phenyl ketone 7a, p-toluyl ketone 7b, biphenyl ketone 7c and -naphthyl ketone 7d) is reported. The aryl ketone 7a, 7b and 7c undergo photo-racemization with efficiencies of 0.75, 0.79 and 0.76 respectively on direct irradiation. Direct irradiation of the ketone 7d, however, undergoes 1,3-shift with an efficiency of 0.02. Triplet states are responsible for the racemizations and singlet state is responsible for 1,3-shift as in general. The ketone 7a, 7b and 7c are good example of a few ${\beta},{\gamma}$-unsaturated ketones which undergo efficient intersystem crossing on direct irradiation.

• Bulletin of the Korean Chemical Society
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• v.19 no.2
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• pp.243-249
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• 1998

The reaction of alcohol with a solution of thexylborane (ThxBH2) in tetrahydrofuran (THF) provides a new class of mild and selective reducing agents, thexylalkoxyboranes (ThxBHOR: R=Et, i-Pr, i-Bu, s-Bu, t-Bu, Ph). In order to elucidate the effect of the alkoxy group in reduction reactions, the reducing power of ThxBHOR toward selected organic compounds containing representative functional groups under practical conditions (THF, 25°, the quantitative amount of reagent to compound) has been investigated. Generally, the reactivity of ThxBHOR is largely dependent upon the alkoxy substituent. ThxBHOR can be synthesized from a variety of alcohols, thus allowing control of the steric and electronic environment of these reagents.