• Bulletin of the Korean Chemical Society
• /
• v.26 no.12
• /
• pp.1981-1985
• /
• 2005

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.6
• /
• pp.1907-1911
• /
• 2011

A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.

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

• Journal of the Korean Chemical Society
• /
• v.46 no.4
• /
• pp.323-330
• /
• 2002

The protonation equilibrium of 5-substituted 2-furaldehydes is investigated spectrophotometrically in aqueous sulfuric acid at $25^{\circ}C$ and the basicity constants(p$K_{BH+}$) of the substrates is calculated by means of the excess acidity method. The basicity constant of 5-metyl-2-furaldehyde having electron donating group is larger than that of 5- nitro-2-furaldehyde having electron withdrawing group. Difference between the basicity constants(p$K_{BH+}$) of these two compounds was about 3.25 pK unit. The m value which is the degree of solvation of the protonated substrate is similar to that of acetophenone having same protonation site. The dependence of p$K_{BH+}$ on m value shows good linear cor-relation.

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

• Journal of the Korean Chemical Society
• /
• v.21 no.1
• /
• pp.38-43
• /
• 1977

The rate constant of the reaction of 3-or 4-substituted pyridines with benzyl benzenesulfonate in acetone at $35^{\circ}C$ were determined by an electric conductivity method. According to the Hammett plot, the rates were increased the electron donating ability at the $S_N2$ reaction of benzyl benzenesulfonate with pyridine and 4-$NH_2$ pyridine was correlated with ${\sigma}^+$ than Hammett ${\sigma}$ value. This result was explained that $NH_2$ group and N atom in pyridine are largely contribute by resonance. In Br$\"{o}$nsted plot, 4-amino and electron attracting group were deviated from the increasing part at linearity. It was considered to solvent effects on substituents. A mechanistic possibility was proposed to account for the results. Some activation parameters were also calculated.

• Journal of the East Asian Society of Dietary Life
• /
• v.17 no.3
• /
• pp.384-392
• /
• 2007

The primary objective of this study was to determine the effects of a water-distilled extract with 15 kinds of Korean medicinal herb on antioxidant activity, antimicrobial activity against Helicobacter pylori, and lipid metabolism. The water-distilled extract (WE) and fermenting water-distilled extract (FE) of medicinal herbs were utilized in order to make functional beverages. The EDA (electron donating activity), SOD-like ability, and RAE (relative antioxidant efficacy) of WE averaged 24.47, 50.35, and 1.57%, respectively, but the EDA, SOD-like ability, and RAE of FE was retardeded by 12.01, 35.72, and 1.55%, respectively. The antimicrobial activity against Helicobacter pylori of WE averaged 12.84 mm as a diametric clear zone, and was significantly (p<0.05) higher than those measured in the WE and control. Serum triglyceride contents, total serum cholesterol contents, and serum LDL-cholesterol contents of the WE group were significantly (p<0.05) lower than those of the control group. The liver total-cholesterol contents and liver triglycerides of WE group were significantly (p<0.05) lower than those of the control group. The plasma TBARS value of the WE group was significantly (p<0.05) lower than that of the control group. The sensory evaluation, taste, and smell of FE were more desirable than those of WE, but the color of WE was more desirable. According to the above results, the water distilled extracts (WE) of 15 kinds of medicinal herb are supposed to be effective with regard to antioxidant activity and lipid metabolism, but the antimicrobial activity against Helicobacter pylori was increased as the result of fermentation.

• Journal of Photoscience
• /
• v.11 no.32
• /
• pp.71-74
• /
• 2004

The macrocycle L exhibited a switch on-off behavior through the fluorescent responses by aromatic imine molecule 1 (X=H) / trifluoroacetic acid (TFA). In the 'switch on' state, it was supposed that the aromatic imine molecule 1 is in the cavity of macrocycle L and a photoinduced electron transfer (PET) from the nitrogen of azacrown part to the anthryl group is inhibited by the interaction between the aromatic imine molecule 1 and the azacrown part of macrocycle L. In the 'switch off' state, it was supposed that the protonated imine molecule 1 is induced by the continuous addition of TFA and a repulsion between the protonated azacrown part and the protonated imine molecule 1 is occurred. It was considered that this process induces the intermolecular PET from the protonated imine molecule 1 to the anthryl group of macrocycle L because of a proximity effect between the anthryl group and the protonated imine molecule 1. From the investigation of the transient emission decay curve, the macrocycle L showed three components (3.45 ns (79.72%), 0.61 ns (14.53%), and 0.10 ns (5.75%). When the imine molecule 1 was added in the macrocycle L as molar ratio=1:1, the first main component showed a little longer lifetime as 3.68 ns (82.75%) although the other two components were similar as 0.64 ns (14.28%) and 0.08 ns (2.96%). On the contrary, when the imine molecule 3 (X=C1) was added in the macrocycle L as molar ratio=l:1, all the three components were decreased such as 3.27 ns (69.83%), 0.44 ns (13.24%), and 0.06 ns (16.93%). The fluorescent pH titration of macrocycle L was carried out from pH=3 to pH=9. The macrocycle L and C $U^{2+}$- macrocycle L complex were intersected at about pH=5, while the E $u^{3+}$ -macrocycle L complex was intersected at about pH=5.5. In addtion, we investigated the fluorescence change of macrocycle L as a function of the substituent constant ($\sigma$$_{p}$$^{o}$) showing in the para-substituent with electron withdrawing groups (X=F, Cl) and electron donating groups (X=C $H_3$, OC $H_3$, N(C $H_3$)$_2$), respectively, as well as non-substituent (X=H).).ctively, as well as non-substituent (X=H).

• Archives of Pharmacal Research
• /
• v.23 no.6
• /
• pp.579-584
• /
• 2000

To explore the effect of substituents' on phenyl motif on sulfonyl function of novel anticancer 4-phenyl-1-benzenesulfonylimidazolidinones (1), electron donating or withdrawing sub-stituents were introduced at 3 or 4-position and the analogs were tested against human lung (A549) and colon (HCT-15) cancer cell lines. Quantitative structure activity relation-ship of the 4-substituted series shows that only STERIMOL L values are well correlated. The increment of substituent's volume enhances the activity against both cell lines. The small substituent at 3-position additionally increases the activity. However naphthyl group in place of phenyl reduces the activity, Therefore the phenyl motif with sterically large substituent at 4-position and small substituent at 3-position may be important for their activity. Integration of these substituents' effects into the structural design led to discover the more potent analog, 4-phenyl-1-(N-acetylindoline-5-sulfonyl) imidazolidinone (1n).

• Proceedings of the Korean Vacuum Society Conference
• /
• 2016.02a
• /
• pp.197-197
• /
• 2016

Quantum dot nanocrystals(QDs) have been emerged as next generation materials in the field of energy harvesting, sensor, and light emitting because of their compatibility with solution process and controllable energy band gap. Especially, characteristics of color tuning and color purity make it possible for QDs to be used photoluminescence materials. Photoluminescence devices with QDs have been researched for a long time. Photoluminescence quantum yield(PL QY) is important factor that defines the performance of Photoluminescence devices. One of the ways to achieve better PL QY is ligand modification. If ligands are changed to proper electron donating group, electrons can be confined in the core which results in enhancement of PL QY. Because of the reason, short ligands are preferred for enhancing PL QY. Thiophenol-based ligands are shorter than typical alkyl chain ligands. In this study, the effect of thiophenol-based ligands with different functional groups are investigated. Four different types of thiophenol-based organic materials are used as organic capping ligand. QDs with bare thiophenol and fluorothiophenol show better quantum yield compared to oleic acid.