• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1297-1304
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• 2006

A systematic study of the structure, energetics and spectral characteristics of substituted aminoketenes $R(NH_2)$C=C=O (R = H, $CH_3$, $NH_2$, OH, $OCH_3$, CH=$CH_2$, C$\equiv$CH, CN, CHO, NO, $NO_2$) which are highly reactive and transient intermediates in synthesis has been conducted by ab initio calculations at the MP2/6- 31G*//MP2/6-31G* level. Twenty four stable isomers of the eleven substituted aminoketenes having dihedral angles $\phi NH_2\sim120{^{\circ}}$ and $60^{\circ}$ have been identified and their optimized geometries and energies obtained. Electrostatic and steric effects on the molecular geometries have been analyzed. While the $\pi$-acceptor groups lead to planar conformations, the electron-donor groups give rise to non-planar conformations. Isodesmic substituent stabilization energies relative to alkenes have been calculated and correlation with group electronegativities established. Role of induction effect by the substituent groups and resonance effects in charge distribution in the molecules has been analyzed. An analysis of the asymmetric stretching frequencies and intensities of the C=C=O group shows that affect of non-$\pi$ acceptor substituents on the frequency is determined by the field effect (F) and resonance effect (R) parameters, the calculated intensities I (km/mol.) are correlated to group electronegativities $x$ of the substituents by the relationship I = 640.2–100.1 $x$ (r = 0.92). The $\pi$-acceptor substituents increase the intensity which may be explained in terms of their delocalizing effect on the negative charge at the $C_{\beta}$ atom.

• Bulletin of the Korean Chemical Society
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• v.26 no.5
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• pp.795-801
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• 2005

New PPV derivatives which contain electron-withdrawing trifluoromethyl ($CF_3$) group, poly[2-(2-ethylhexyloxy)-5-(4-trifluoro methylphenyl)-1,4-phenylenevinylene] (EH$CF_3$P-PPV), and poly[2-(2-ethylhexyloxy)-5-(3,5-bis(trifluoromethyl)-phenyl)-1,4-phenylenevinylene] (EHB$CF_3$P-PPV), have been synthesized by GILCH polymerization. As the result of the introduction of the electron-withdrawing $CF_3$ group to the phenyl substituent, the LUMO and HOMO energy levels of EH$CF_3$P-PPV (2.8, 5.1 eV) and EHB$CF_3$P-PPV (3.0, 5.3 eV) were lower than those of known poly[2-(2-ethylhexyloxy)-5-phenyl-1,4-phenylenevinylene] (EHP-PPV) (2.6, 4.9 eV). These polymers have been used as the electroluminescent (EL) layers in double layer lightemitting diodes (LEDs) (ITO/PEDOT/polymer/Al). EH$CF_3$P-PPV, and EHB$CF_3$P-PPV show maximum photoluminescence (PL) peaks at ${\lambda}_{max}$ = 550, 539 nm, and maximum EL peak at ${\lambda}_{max}$ = 545, 540 nm, respectively. The current-voltage-luminance (I-V-L) characteristics of the polymers show that turn-on voltages of EH$CF_3$P-PPV and EHB$CF_3$P-PPV are around 4.0 and 3.5 V, respectively.

• Journal of the Korean Chemical Society
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• v.31 no.2
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• pp.133-142
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• 1987

Stereoselectivities of (4+2) cycloaddition reactions of cyclopentadiene with the methyl-substituted allenic acids and esters were investigated by application of $\pi$-nonbonded interaction ($\pi$-NBI) theory. 2-FMO method has been found to be adequate for determination of endo selectivities of diene(LUMO)-dienophile (LUMO) interaction in the thermal reactions and diene (HOMO)-dienophile (LUMO) interaction in the Lewis acid catalyzed reactions. $\pi$-isoconjugate diene structure was formed by through-bond interaction of allene moiety with methyl group in the cumulated diene system; the methyl substituent acts as a conjugative chain and causes inter-level narrowing effect of the FMO's. In dienophiles which do not form $\pi$-isoconjugate diene system, methyl group acts merely as an electron donating group. In thermal reactions, the stereoselectivities are controlled by $\pi$-nonbonded secondary orbital interaction ($\pi$-NSOI) of methyl substituent, which behaves similarly as an ethylene molecule.

• Applied Biological Chemistry
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• v.37 no.4
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• pp.287-294
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• 1994

New 3-phenyl-1-(2-furyl)propenones, 1 and 3-phenyl-1-(2-furyl)-3-thiophenyl-propanone, 2 derivatives were synthesized, and their fungicidal activities in vitro against Botrytis cineria (BC), Valsa ceratosperma (VC), Scelerotium cepivorum (SC) and Phytophthora capsici (PC) were investigated using a generalized structure-activity relationship (SAR). The activity of 1 was superior to those of 2, and nonsubstituent, 1a and chloro group substituent, 1d of E (Syn) conformer were the most effective $(EC_{50}=10{\sim}12\;ppm)$ compound to BC. Antifungal activities were able to predict to depend essentially on the ${\beta}$ carbon and their positive charge from the results that the good correlation $(r^2=0.90)$ was observed between hydrolysis rate constant (logk) of 1 and the electronic parameter $({\sigma})$ of X-substituent on the ${\beta}-phenyl$ ring.

• Applied Biological Chemistry
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• v.37 no.6
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• pp.516-521
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• 1994

New seventeen imazapyr derivatives, 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-(N-methyl-N-X(sub.)-phenylaminooxoacetyl)pyridine, 6 were synthesized and their pre-emergence herbicidal activity$(pI_{50})$ in vivo against Corn (Zea mays L.) and Pigweed (Amaranthus viridis L.) were studied by the pot test under paddly conditions. Quantitative structure activity relationships (QSARs) were analyzed using the physicochemical parameters of substituent(X) on the phenyl ring of 3-(N-methyl-N-X(sub.)-phenylaminooxoacetyl) group and regression analysis. The herbicidal activities were related to the steric effect of X-substituent. The effect was rationalized by paraholic function of MR and $L_1$, where the optimal values were MR=5.56 (Zea mays L.) and $L_1=3.34\;{{\AA}}$ (Amaranthus viridis L.). Among them, 2,5-difluoro substituted compound, 6i showed good herbicidal activity against Pigweed with excellent tolerance to Corn.

• Applied Biological Chemistry
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• v.42 no.3
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• pp.252-255
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• 1999

Inhibition activities$(pI_{50})$ of chalcone derivatives as substrate with farnesyl protein transferase(FPTase) were determined in vitro. The structure activity relationships(SAR) between the activity and physicochemical parameters of X & Y-substituents on the phenyl groups were analyzed by Free-Wilson and Hansch method. X-substituents on the benzoyl group have the more important role to inhibition activity than Y-substituents on the styryl group. Among them, none substituent, 8 showed the highest FPTase inhibition activity$(pI_{50}=4.30)$. Particularly, the SAR equation could be formulated, showing a parabolic relationship between the activity and hydrophobicity(logP) where the optimal value$({\Sigma}logP)_{opt}$ was 3.915. And also the activity depends on the steric effect(Es > 0) with X-substituent and the resonance effect(R < 0) with electron donating Y-substituents. Based on the results of SAR analyses, the interactions between substrates and receptor, FPTase, could be assumed.

• Applied Biological Chemistry
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• v.51 no.3
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• pp.219-222
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• 2008

In the search for third generation herbicidal cyclic imide derivatives, the average values of herbicidal activity ($pI_{50}$) in vivo (pre-emergence) of 40 new peroxidizing herbicides, 1-(4-chloro-2-fluoro-5-propargyloxyphenyl)thiourea derivatives (1-40) against rice plant (Orysa sativa) and barnyard grass (Echinochlor crus-galli) were studied. The molecular similarity between protoporphyrinogen IX (protogen) as the substrate of protox enzyme and Urea derivatives (1-40) was discussed quantitatively. The diallyl (20) and 3-nitro substituent (33) showed the selective herbicidal activity against barnyard grass. Allyl substituent (8) and their molecular similarity in dice (S=0.81) showed the highest levels of herbicidal activity ($pI_{50}$=4.71). Also, similarity indices (S) and superimposed volume (C) of protogen and aryl-substituents (21-40) showed good correlation.

• Applied Biological Chemistry
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• v.41 no.6
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• pp.471-476
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• 1998

A synthesis and the screening of new 2-iminothiazolines (IV) of which structures are modified based on a lead compound, thiazoline for development of new agrochemical fungicide were described. Bromination of acetoacetanilides (I) which were prepared by the reaction of diketene with anilines gave the corresponding ${\gamma}-bromoacetoactanilide\;(II)$. Treatment of II with N-phenyl-N'-methyl thiourea (III) afforded IV, structure of which was confirmed by various spectroscopic methods. Antifungal activity of the new IV was tested against six kinds of typical plant diseases (in vivo). The IV with aromatic substituents showed remarkable activity against the Pyricuraria oryzae at 250 ppm in primary screening. The candidates with control value over 90% in primary screening were selected and further tested for second screening at lower concentrations. The IV which has an electron-withdrawing substituent such as halogen, especially fluorine in aryl group showed a higher activity as compared to those with electron-donating group and meta substituent was for optimal position.

• Applied Biological Chemistry
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• v.38 no.1
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• pp.90-94
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• 1995

Post emergence herbicidal activities$(pI_{50})$ of X-substituted phenylvinylsulfone derivatives(S) in-vivo against rice(Oryza sativa L.), Barnyard grass(Echinochloa crus-galli) and Pickerelweed(Monochoria vaginalis Presl) were measured by the pot test under paddy conditions. The (S) showed herbicidal symptom rapidly with lower activity(average $pI_{50}=2.0$) as proherbicide, which was excellent tolerance to rice. The structure activity relationships(SAR) were analyzed using such a physicochemical parameters as hydrophobic$({\pi})$ and molecular orbital(MO) quantity by the multiple regression technique, and discussed with quantum pharmacology. The herbicidal activities were related to the hydrophobic$({\pi})$ effect of X-substituent and orbital(HOMO & LUMO) energy. In case of Pickerelweed, the effect was rationalized by parabolic function of ${\pi}$ constant, where the optimal value of ${\pi}$ was 1.10. An increase in hydrophobicity and negative orbital energy by the electron attracting X-substituent may contribute to the herbicidal activity. Based on results proposed from SAR analysis, the mode of herbicidal action could be assumed.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1749-1753
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reaction of Y-substituted-phenyl picolinates (7a-f) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOK] curves upward while the plot of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ is linear with a positive intercept in all cases. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOK}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ ion and ion-paired EtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The ${\sigma}^{\circ}$ constants result in a much better Hammett correlation than ${\sigma}^-$ constants, indicating that the reaction proceeds through a stepwise mechanism in which departure of the leaving group occurs after the rate-determining step (RDS). $K^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through formation of a cyclic transition state (TS). The catalytic effect decreases as the substituent Y becomes a stronger electron-withdrawing group (EWG). Development of a positive charge on the N atom of the picolinyl moiety through resonance interactions is responsible for the decreasing $K^+$ ion catalysis.