• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1722-1726
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• 2013

A kinetic study on nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5j) with ethylamine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of $k_{obsd}$ vs. [amine] are linear for the reactions of substrates possessing a strong electron-withdrawing group (EWG) but curve upward for those of substrates bearing a weak EWG, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. The reactions have been concluded to proceed through a stepwise mechanism with one or two intermediates (a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$) depending on the nature of the substituent Y. Analysis of Bronsted-type plots and dissection of $k_{obsd}$ into microscopic rate constants have revealed that the reactions of substrates possessing a strong EWG (e.g., 5a-5f) proceed through $T^{\pm}$ with its formation being the rate-determining step, while those of substrates bearing a weak EWG (e.g., 5g-5j) proceed through $T^{\pm}$ and $T^-$.

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.851-855
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• 2008

The reactions of O,O-diphenyl Z-S-phenyl phosphorothiolates with X-pyridines have been studied kinetically in acetonitrile at $35.0{^{\circ}C}$. The Hammett plots for substituent (Z) variations in the leaving group (log $k_2$ vs. $\sigma$ Z) are biphasic concave downwards with breaks at Z = H. The large magnitudes of ${\rho}X(\rho_{nuc})$, ${\beta}X(\rho_{nuc})$, and the cross-interaction constant, $\rho$XZ, suggest frontside nucleophilic attack toward the leaving group. The sign reversal of $\rho$Z from positive in $\sigma$ Z $\leq$ 0 to negative in $\sigma$ Z $\geq$ 0 is interpreted as the change in mechanism from concerted to stepwise with rate-limiting expulsion of the leaving group. The anomalous negative sign of $\rho$ Z for leaving groups with electron-withdrawing substituents is interpreted as the intramolecular ligand exchange process of the leaving group from the equatorial position in the intermediate to the apical position in the TS.

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.3081-3089
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• 2011

A series of new bis-thienylanthracene derivatives D1~D5 containing 9,10-antharcene moiety in the center and 2-methylenemalonotitrile or 2-cyanoacrylic acid functional group on the terminal thiophenes were synthesized and characterized by $^1H$-NMR and high-resolution mass spectroscopy. Their optical, electrochemical, and thermal properties were measured. They have absorption ${\lambda}_{max}$ in the range of 437~480 nm and max of $7.4{\times}10^3{\sim}2.0{\times}10^4M^{-1}cm^{-1}$. The substitution of 2-cyanoacrylic acid group allows greater value of ${\varepsilon}_{max}$ than that of 2-methylenemalonotitrile. TGA curves showed that D4 and D5 which have 2-cyanoacrylic acid functional group on the terminal thiophene(s) exhibit good thermal stability and D4 was thermally stable up to $400^{\circ}C$. Their optical properties and LUMO energy levels measured suggest that they can serve as potential candidates for electron donor materials of organic photovoltaic cells (OPVs) or D4 and D5 which contain 2-cyanoacrylic acid group can be used as organic dyes of dye-sensitized solar cells (DSSCs).

• Journal of Applied Biological Chemistry
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• v.49 no.3
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• pp.101-105
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• 2006

Degradation of the herbicide butachlor was investigated using laboratory-synthesized zerovalent iron ($Fe^0$). The synthesized zerovalent iron was determined to be nanoscale powder by scanning electron microscopic analysis. To investigate degradation of butachlor using the synthesized nanoscale zerovalent iron, time-course batch experiments were conducted by treating the solution of butachlor formulation with the iron. More than 90% degradation of butachlor was observed by iron treatment within 24 h. The synthesized nanoscale zerovalent iron showed an increase in particle aggregation in the batch tests. Green rust formation and a pH drop in solutions were observed, suggesting that the oxidation of the iron occurred. When the iron was extracted with dichloromethane, a negligible concentration was found in the extract, suggesting that butachlor did not bind to the iron particles. GC/MS analysis detected the dechlorinated product as a major degradation product of butachlor in the solutions. The data indicate that laboratory-synthesized zerovalent iron functioned as a reductant to remove electron-withdrawing chlorine, giving the dechlorinated product.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1309-1313
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• 2010

The effects of boronic acid on the fluoride-selective chemosignaling behavior of a merocyanine dye were investigated. In the presence of phenylboronic acid (PBA), N-methylquinolinium-based merocyanine dye displayed fluoride-selective chromogenic signaling behavior over other commonly coexisting anions in the micromolar concentration range. Signaling is produced by a fluoride-induced displacement of the dye from its complex with PBA, resulting in a significant chromogenic signal for the fluoride ion. This signaling was successfully analyzed using a ratiometric analysis of the UV-vis absorption in response to changes in fluoride ion concentration. A PBA substituted with an electron withdrawing group was found to exhibit a more pronounced signal. Polymer-bound PBA also exhibited useful fluoride-selective signaling behavior.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.34-43
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• 1980

The reaction of thianthrene cation radical perchlorate with thioxanthene in acetonitrile gave thianthrene and dark reddish thioxanthylium ion instead of thioxanthene cation radical. Addition of aromatic nucleophiles such as anisole, aniline, N,N-diethylaniline, catechol, ethylbenzene, to the above mixture yielded the corresponding thioxanthenes with substituent at 9 position. Reactions with dibenzo-18-crown-6-ether, diphenylmercury, and triphenylphosphine gave similar products. However, reactions with aromatics with electron-withdrawing group were either too slow or inert to such a reaction.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.37-40
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• 1965

7-Nitro-8-hydoxyquinoline-5-sulfonate (NHQS) have been synthesized from 8-hydroxyquinoline-5-sulfonic acid by nitrosation in alkaline medium at temperature below $10^{\circ}C$ and the acid dissociation constants of NHQS have been determined by spectrophotometric and potentiometric methods. Almost same values are obtained by both methods but the values are lower than the corresponding 8-hydroxyquinoline. The lower basicity of NHQS is considered as the effect of electron withdrawing groups, especially adjacent nitroso group.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1754-1758
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• 2014

The nucleophilic substitution reactions of bis(Y-aryl) chlorothiophosphates (1) with X-pyridines are investigated kinetically in acetonitrile at $35.0^{\circ}C$. The free energy relationships with both X and Y are biphasic concave upwards with a break point at X = 3-Ph and Y = H, respectively. The sign of cross-interaction constants (CICs; ${\rho}_{XY}$) is positive with all X and Y. Proposed mechanism is a stepwise process with a rate-limiting leaving group departure from the intermediate with all X and Y. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). In the case of Y = electron-withdrawing groups, the cross-interaction between Y and Y, due to additional substituent Y, is significant enough to change the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1, indicative of the change of mechanism from a rate-limiting bond formation to bond breaking.

• Journal of Photoscience
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• v.8 no.1
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• pp.23-25
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• 2001

The methyl pheophorbide-a (MP-a) and methyl pyropheophorbide-a (MPP-a) were modified by reaction of exocyclic ketone in E-ring with nucleophilic reagent and several chlorin derivatives were synthesized. The change of the structure in E-ring served an expanding conjugation region and introduction of electron-withdrawing group, which strongly influenced the visible spectra. The Qy bands of synthesized compounds were affected by the substituents on the Qy axis(N$\sub$21/-N$\sub$23/).

• Journal of Photoscience
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• v.11 no.3
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• pp.107-113
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• 2004

Synthesis, absorption and fluorescence properties of 3-methyl indole (1), N-(benzenesulfonyl)-3-(3-oxo-but-1-enyl)-indole (2) and 1H-3-(3-oxo-but-1-enyl)-indole (3) are described. Extended conjugation at C-3 of indole as in 3 causes moderate resolution of $^1L_a$ and $^1L_b$ bands. However, 2 having an electron-withdrawing group at indolic nitrogen shows only the $^1L_a$ band. While the $^1L_b$ band largely remains solvent polarity independent, the $^1L_a$ band undergoes moderate red shift in polar solvents. The fluorescence in 2 and 3 originates from the $L_b$ transition. Additionally, interaction of 2 and 3 with BSA indicates that these compounds bind to the hydrophobic site of BSA with the formation of a highly fluorescent BSA-probe complex.