• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2983-2988
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• 2013

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-chloro-2-nitrophenyl X-substituted-benzoates (1a-1h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 1a-1h with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X $ = 1.25 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step (RDS) but is caused by ground-state stabilization through resonance interactions for substrates possessing an electron-withdrawing group in the benzoyl moiety. The Br${\o}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (1d) with a series of cyclic secondary amines curves downward with ${\beta}_2$ = 0.85, ${\beta}_1$ = 0.24, and $pK_a{^o}$ = 10.5, implying that a change in RDS occurs from the $k_2$ step to the $k_1$ process as the $pK_a$ of the conjugate acid of the amine exceeds 10.5. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio associated with the reaction of 1d reveals that $k_2$ is dependent on the amine basicity, which is contrary to generally held views.

• Bulletin of the Korean Chemical Society
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• v.10 no.6
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• pp.619-620
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• 1989

• Fibers and Polymers
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• v.2 no.3
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• pp.129-134
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• 2001

Liquid crystalline (LC) poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate) (50/50, mole/mole) [PECPT] was synthesized and blended with polycarbonate (PC). LC properties of PECPT and thermal, morphological, and rheological behaviors of the PECPT/PC blend were studied. PECPT showed the nematic LC phase and much longer relaxation time than poly(ethylene terephthalate) (PET). The apparent melt viscosity of PECPT was one third of that of FET. An abrupt torque change was observed during the blending process due to the orientation of LC domains. For the blends containing 10~30 wt% of PECPT, the complex viscosities were higher than that of PC. As PECPT content increases above 40 wt%, shear thinning was observed. The lowest complex viscosity was obtained at 40~50 wt%. Transesterification of PECPT and PC was confirmed by the selective chemical degradation of carbonate groups in PC.

• Journal of the Korean Magnetic Resonance Society
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• v.2 no.1
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• pp.66-83
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• 1998

Study on spin-rotation relaxation of nuclear spins located on a methyl group can reveal valuable dynamic information related to the internal rotation of methyl group itself. Toward this end we have measured methyl carbon-13 spin-rotation of methyl group itself. Toward this end we have measured methyl carbon-13 spin-rotational relaxation rate in toluene and 2-chloro-p-xylene over the temperature range of 179-363K. To interpret the temperature dependence of measured spin-rotational relaxation rate we have revised the temperature dependence of measured spin-rotational relaxation rate we have revised the expression derived thus far by other authors and reproduced experimental data on the basis of the newly derived expression. The results confirmed that our expression leads to better agreement with experimental data than the previous one over observed temperature range, especially at high temperature.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.551-556
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• 2014

The treatment of alkylated nitro derivatives of indazole with 2-(4-chlorophenyl)acetonitrile under basic conditions gave the new 8-chloro-3-alkyl-3H-pyrazolo[4,3-a]acridine-11-carbonitriles via the nucleophilic substitution of hydrogen which proceeds at room temperature with concomitant cyclisation in fairly good yields. The structures of all newly synthesized compounds were confirmed by IR, $^1H$ NMR, $^{13}C$ NMR and mass spectral data. Fluorescence experimental results of all newly synthesized compounds revealed remarkable photoluminescence properties and strong green fluorescence properties. Also, the new compounds exhibited potent antibacterial activity and their antibacterial activity (MIC) against Gram positive (Staphylococcuse aureus methicillin resistant S. aureus and Bacillus subtilis) and negative bacterial (Pseudomonas aeruginosa and Escherichia coli) species were determined.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.436-440
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• 2014

The ${\alpha}$-Effect; Ground state; Transition state; Intramolecular H-bonding; Yukawa-Tsuno plot; Second-order rate constants for aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (1a-h) have been measured spectrophotometrically in 80 mol % $H_2O/20$ mol % DMSO at $25.0^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (1d) with a series of primary amines curves downward, which has been taken as evidence for a stepwise mechanism with a change in rate-determining step (RDS). The Hammett plots for the reactions of 1a-h with hydrazine and glycylglycine are nonlinear while the Yukawa-Tsuno plots exhibit excellent linearity with ${\rho}_X=1.22-1.35$ and ${\gamma}= 0.57-0.59$, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by stabilization of substrates possessing an electron-donating group (EDG) through resonance interactions between the EDG and C=O bond of the substrates. The ${\alpha}$-effect exhibited by hydrazine increases as the substituent X changes from a strong EDG to a strong electron-withdrawing group (EWG). It has been concluded that destabilization of hydrazine through the electronic repulsion between the adjacent nonbonding electrons is not solely responsible for the substituent dependent ${\alpha}$-effect but stabilization of the transition state is also a plausible origin of the ${\alpha}$-effect.

• The Korean Journal of Pesticide Science
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• v.8 no.3
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• pp.175-183
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• 2004

The characteristics of the experimental compound EK-5439 [3-Chloro-2-[4-chloro-2-fluoro-5-(5-methyl-3-phenyl-4,5-dihydroisoxazol-5-yl-methoxy)-phenyl]-4,5,6,7-tetrahydro-2H-indazole] was investigated to characterize as a new herbicide to use in rice field. The selectivity between rice and barnyardgrass was very good when treated from 0 to 4 days after seeding under soil application. In the overflowing experiment, herbicidal efficacy of EK-5439 was stabilized 12 hrs after application. Vertical migrations in submerged paddy soil of EK-5439 and oxadiazon were equally observed below a soil depth of 1 cm under 5 cm/day leaching condition. Half-lives for herbicidal efficacy of EK-5439 and oxadiazon were 6.1, and 9.6 days, respectively, under submerged paddy condition. EK-5439 showed rapid adsorption to the soil clay, such as bentonite.

• The Korean Journal of Pesticide Science
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• v.10 no.4
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• pp.262-265
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• 2006

A series of N-[4-chloro-2-fluoro-5-(2-(substituted)pyrimidinyloxy)phenyl]-3,4,5,6-tetrahydrophthalimides was synthesized, and the herbicidal activities of those derivatives were evaluated through pre- and post-emergence application under upland conditions in a greenhouse. The results showed that most compounds resulted in stronger herbicidal activities on broadleaf weeds than on grass weeds. The N-[4-chloro-2-fluoro-5-(2-pyrimidinyloxy)phenyl]-3,4,5,6-tetrahydrophthalimide showed the best weed control efficacy and marginal corn safety at a rate of 60 g/ha through pre-emergence application.

• The Korean Journal of Pesticide Science
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• v.8 no.2
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• pp.79-87
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• 2004

3-Chloro-2-[4-chloro-2-fluoro-5-(5-methyl-3-phenyl-4,5-dihydroisoxazol-5-ylmethoxy)-phenyl]-4,5,6,7-tetrahy dro-2H-indazole(EK-5439) demonstrated rice selectivity and herbicidal activity on annual weeds, such as Echinochloa oryzicola, Monochoria vaginalis, Lindernia pyxidaria, Rotala indica, Aneilema keisak, Cyperus difformis, and Ludwigia prostrata at doses of 16-63 g a.i./ha. However, the application window was limited from pre-emergence to 5 days after transplanting. The control efficacy of EK-5439 on barnyardgrass was 4 times higher than that of oxadiazon. EK-5439 was excellently safe to the 16 different transplanted rice cultivars treated 2 days after transplanting. These compounds have the mechanism of action on the chlorophyll biosynthesis like protoporphyrinogen IX oxidase inhibitors.

• BMB Reports
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• v.29 no.2
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• pp.111-115
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• 1996

A novel glutathione S-transferase from Pseudomonas sp. DJ77 was expressed in E. coli and purified by glutathione-affinity chromatography. The enzyme was composed of two identical subunits. The molecular size of the enzyme was 42 kDa by sephadex G-150 gel permeation chromatography and Mr of each subunit was 23 kDa by sodium dodecylsulfate-polyacrylamide gel electrophoresis. pI value of the enzyme was approximately 5.8 by isoelectric focusing. This enzyme showed the highest activity toward 1-chloro-2,4-dinitrobenzene as the electrophilic substrate. The relative activities toward p-nitrobenzyl chloride and 1,2-dichloro-4-nitrobenzene were 3.8% and 1.3% of the activity toward 1-chloro-2,4-dinitrobenzene, respectively. $K_m$ and $V_{max}$ values for 1-chloro-2,4-dinitrobenzene calculated by Lineweaver-Burk plot were 0.76 mM and $14.81\;{\mu}mol/min/mg$, respectively, and those for glutathione were 6.23 mM and $64.93\;{\mu}mol/min/mg$, respectively. The enzyme showed highest glutathione S-transferase activity at pH 8.0 and was stable between pH 6.0 and 9.0. The enzyme retained its activity up to $35^{\circ}C$ for 90 min but was unstable above $45^{\circ}C$.