• Journal of the Korean Chemical Society
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• v.34 no.5
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• pp.490-497
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• 1990

Two synthetic routes for the 1,4-diboracyclohexene-2 ring 8 have been developed. Method i) starts with 1,2-bis(dichloroaluminyl)ethane, in which the AlCl$_2$ group is replaced by BCl$_2$. Exchange of the chlorine with BI$_3$ in 1,2-bis-(dichloroboryl)ethane yields the corresponding iodo compound, which reacts with the alkynes to heterocycles 8a, b in good yield. In method ii) B$_2$Cl$_4$ is added to alkenes, replacement of chlorine with BI$_3$ yields the bis(diiodoboryl)ethane derivatives which undergo redox reactions with alkynes to give 8c, d. The diiodo derivative 8a forms the pyridine adduct 9a, and reacts with ether to give the ethoxy derivative 8f. 8a-d react with AlMe$_3$ to yield the corresponding dimethyl derivatives 8g-j, which give unstable radical anions when treated with potassium in THF. The ESR parameters are reported. In electrochemical experiments irreversible reductions of 8g-j are observed. 8g-j react with (C$_5$H$_5$)Co(C$_2$H$_4$)$_2$ to give the intermediate 16 VE complexes (C$_5$H$_5$)Co(8), in which C-H activation occurs with formation of the corresponding red 1,4-diboracyclohexadiene complexes 10. The X-ray structure analyses of 10h and 10j are reported.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.105-111
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• 1993

The stability constants for lanthanides complexes with optically active L-proline (1 : 1) were determined in aqueous solution in the ionic medium of 0.1 M $NaClO_4$ at 25$^{\circ}C$ using a pH titration method. The results show called "gadolinium break" between lighter and heavier lanthanides. The linear relation between the stability constant (log$\beta$1) and the pKa values of ligands indicates that L-proline acts as a bidentate ligand in the complexation. The thermodynamic parameters (${\Delta}H$ and ${\Delta}S$) were also determined using an enthalpy titration method at the same condition. The positive endothermic enthalpy change and positive entropy change clearly indicate that the driving force for the complexation is an entropy effect. The comparison of the thermodynamic parameters of L-proline complexes with anthranilate complexes supports the conclusion that the heterocyclic nitrogen atom and carboxylate of L-proline are involved in the chleate formation. The enthalpy values for L-proline are more positive than the ones for anthranilate complex. The difference in enthalpy change for the complex formation between L-proline complex and anthranilate complex is explained in terms of the basicity of the nitrogen donor atom in the ligand. The relatively large entropy change may be described by the extra dehydration related to the rigidity of L-proline ring.

• Korean Chemical Engineering Research
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• v.50 no.4
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• pp.708-712
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• 2012

Ionic liquids (ILs) existing as liquid state at room temperature are composed of a immense heterocyclic cation and inorganic anion which is smaller than cation's size. Thus, the species of cation and anion as well as the length of alkyl group on the cation have influence on their physical properties. Their outstanding properties such as non-volatility, thermal stability and wide range of electrochemical stability make these materials excellent candidates for green solvent which can substitute the conventional organic solvents. In this study, ILs based on imidazolium cation have been synthesized such as 1-butyl-3-methylimidazolium bromide ([BMIM][Br]), 1-butyl-3-methylimidazolium chloride ([BMIM] [Cl]), 1-butyl-3-methylimidazolium iodide ([BMIM][I]), and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][$BF_4$]). The density, viscosity, refractive index, heat capacity and ionic conductivity of [BMIM][Br], [BMIM][I], and [BMIM] [$BF_4$] were measured over range of temperature of 293.2 to 323.2 K. The density and refractive index values of [BMIM][I] were the highest among three ILs and the viscosity values of [BMIM][Br] were the highest among three ILs. The heat capacities [BMIM][$BF_4$] were higher than those of [BMIM][Br]. The ionic conductivities of [BMIM][$BF_4$] were higher than those of [BMIM][I].

• The Korean Journal of Pesticide Science
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• v.2 no.2
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• pp.22-28
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• 1998

Twenty six derivatives of bis-aromatic ${\alpha},{\beta}$-unsaturated ketones as substrate(S) were synthesized and their fungicidal activities in vivo against rice blast(Pyricularia oryzae), tomato leaf blight(Phytophtora infestans) and barley powdery mildew(Erysiphe graminis) were examined. The quantitative structure-activity relationship(QSAR) between the fungicidal activities($pI_{50}$) and a physicochemical parameters of substitued($R_{2}$) phenyl backbone group in 2-thienyl and 2-furyl substituents were analyzed with regression equations. The activities of substituted($R_{2}$) phenyl backbone in 2-thienyl substituents, $1{\sim}10$ would depend largely on the resonance(R>0), molecular refractivity($M_{R}<0$) and optimal length of substituent(($L_{1})opt.=5.50{\AA}$). Whereas, in case of 2-furyl substituents, $10{\sim}26$ optimal molar attraction constant ($F_{opt}=0.49{\sim}l.11$), optimal steric($Es_{opt}=1.78$) constant and indicator variables(Io & Ip) for position of substituents. The fungicidal activity relationship of 2-thienyl substituents against Pyricularia oryzae and Phytophtora infestans have been a reciprocal proportioned.

• The Korean Journal of Pesticide Science
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• v.2 no.2
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• pp.16-21
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• 1998

Bis-aromatic ${\alpha},{\beta}$-unsaturated ketone derivatives represented as substrate(S) were synthesized and their fungicidal activities in vivo against rice blast(Pyricularia oryzae) and tomato leaf blight(Phytophthora infestans) were examined with the quantitative structure activity relationships(QSAR) using 3D QSAR, comparative molecular field analysis (CoMFA). The 3D CoMFA results and those of 2D QSAR were compared and the results reveal that both results show similar trend. The two important factors, steric and electronic, contribute toward the activity. We assumed that fungicidal activity for rice blast was greatly improved by increasing with positive charge of ${\beta}$-carbon and introduction of bulky derivatives into $R_{2}$ group, while that for tomato leaf blight was improved by decreasing the positive charge of ${\beta}$-carbon and introduction of smaller molecular derivative into $R_{2}$ group. The CoMFA analyses clearly demonstrate its potential in unraveling the steric and electronic features of the molecules through contour maps.

• The Korean Journal of Pesticide Science
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• v.9 no.2
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• pp.122-131
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• 2005

For development of new agrochemical fungicide, syntheses of pyrrolo[2,1-b]thiazole carboxanilide derivatives 9 and antifungal screening against 6 kinds of plant pathogens were carried out. Functionalization of carboxylic acid on C-2 into carboxanilide in the pyrrolo[2,1-b]thiazole resulted in new 20 candidates, in which are ${\alpha},{\beta}$-unsaturated carboxanilide and methyl groups that are in cis relationship. Treatment of acetoxy-1,4-thiazin with magnesium in refluxing methanol gave pyrrolo[2,1-b]thiazole ethyl ester 4 in higher yield than that of the previous report. Hydrolysis of this compound afforded the corresponding acid 5, which reacted with aniline derivatives in the presence of coupling reagent, DIC to give pyrrolo[2,1-b]thiazole carboxanilides 9. As the result of in vivo antifungal assay of 9 against rice blast, rice sheath blight, cucumber gray mold, tomato late blight, wheat leaf rust, and barley powdery mildew, some compounds showed selectively antifungal activities against the rice blast and wheat leaf rust.

• Journal of the Korean Chemical Society
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• v.27 no.5
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• pp.330-339
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• 1983

The CNDO/2 and STO-3G calculations were performed on nitrogen, oxygen, and sulfur compounds in order to examine the effect of interactions between two nonbonding (n) orbitals in the same molecule separated by N intervening $\sigma$ bonds based on the PMO approach. Calculated basis level energies, energy splittings, and interaction energy changes for both chain and cyclic model compounds were qualitatively compared with the corresponding predictions derived from perturbational formalism for n-n orbital interactions and successfully explained in terms of the derived energy expressions. In general, through-space interaction term could be neglected in the N and O systems. And the calculated results were explained simply by through-bond interaction term. As a result, through-bond interaction placed n- below n+ for odd systems and n+ below n- for even systems. Also energy splittings in odd systems were larger than those in even systems. However, in the cases of cis-ethylene diamine and o-phenylene diamine(conformer VI in Table 4), through-space interaction term was found to be substantial and the opposing effects of through-space and through-bonds interactions were observed. Finally it was found that the interactions between two n orbitals on S atoms always had some contribution of the destabilizing through-space interaction term. This result was consistent with the fact that the lone pair lobes of third elements were larger in size than those of the second period elements.

• Applied Biological Chemistry
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• v.39 no.3
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• pp.235-240
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• 1996

The most stable stereo conformer in non substituted benzenesulfonyl urea, 1 was the II-keto form, which the molecule was intramolecular associated(H-bond) coformer between imide group and N atom on the Pyrimidine ring. The hydrolytic degradation of 2 derivatives were proceeds by nucleophilic addition reaction(p<0) with orbital controlled intermolecular interaction between LUMO with electron donating$(\sigma<0)$ groups of 2 and HOMO of water molecule. N-(4,6-disub. pyrimid ine-2-yl)aminocarbonyl-2-(1,1-dimethoxy-2-fluoro)ethylbenze nesulfonamides,3 and N-(4,6-disub. triazine-2-yl)aminocarbonyl-2-(1,1-d imethoxy-2-fluoro)ethylbenzenesulfonamides,4 we re synthesized and their herbicidal activities in vivo against bulrush (Scirpus juncoides.) were measured by the pot test under the paddy conditions And the structure activity relationships(SAR) were analyzed by the multiple regression technique. The results of the SAR suggested that the 3 and 4 derivatives indicated dependent on the hydrophobicity of the 4,6-disubstituents and the heterocyclo group, where the optimal value $((log\;P)_{opt.}=0.89)$ of hydrophobicity was 0.89. The pyrimidine substituents, 3 showed higher herbicidal activity than the triazine substituents, 4. Among them, 4,6-dimethoxypyrimidine substituent, 3a showed the best herbicidal activity.