• Bulletin of the Korean Chemical Society
• /
• v.18 no.4
• /
• pp.390-394
• /
• 1997

Nucleophilic substitution reactions of 2-thiopheneethyl benzenesulfonates (2-TEB) and 3-thiopheneethyl benzenesulfonates (3-TEB) with anilines and N,N-dimethylanilines (DMA) are investigated in acetonitrile at 60.0 ℃. The cross-interaction constants ρxz determined for the reactions with anilines are large negative (- 0.50) which are comparable to those for the similar predominantly frontside-attack SN2 reactions of 1-phenylethyl (1-PEB), 2-phenylethyl (2-PEB) and cumyl benzenesulfonates. A large negative ρxz value (- 0.4∼- 0.8) is considered to provide a mechanistic criterion for the frontside-attack SN2 mechanism with a four-center transition state. In agreement with this proposal the kinetic isotope effects, kH/kD, involving deuterated aniline nucleophiles are all greater than one reflecting partial N-H(D) bond cleavage in the transition state. The MO theoretical reactant structures of 1-PEB, 2-PEB and 2-TEB based on the PM3 calculation show that the benzene ring blocks the backside nucleophile approach to the reaction center carbon (Cα) enforcing the frontside-attack SN2 mechanism.

• Journal of Integrative Natural Science
• /
• v.9 no.2
• /
• pp.94-102
• /
• 2016

The crystal structure of the potential active 6-ethoxy-3-phenyl-5a,9a-dihydro-3H-chromen[4,3-c][1,2]oxazole-3a(4H)-carbonitrile ($C_{19}H_{15}N_2O_3$) has been determined from single crystal X-ray diffraction technique. The title compound crystallizes in the monoclinic space group C2/c with unit cell dimension a= 29.3026(9) ${\AA}$, b= 6.7695(2) ${\AA}$ and c= 19.7597(6) ${\AA}$ [${\alpha}= 90^{\circ}$, ${\beta}= 125.709(10)^{\circ}$ and ${\gamma}= 90^{\circ}$]. Single crystals suitable for X-ray diffraction were obtained by slow evaporation method, the isoxazole and six membered pyran rings adopts envelope conformation. The crystal packing of the molecules is stabilized by the weak $C-H{\ldots}N$ hydrogen bond interaction.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.4
• /
• pp.1138-1142
• /
• 2011

Kinetic studies for the reactions of Y-aryl phenyl chlorothiophosphates with X-pyridines have been carried out in acetonitrile at $35.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = 3-Ph, while the Hammett plots for substituent Y variations in the substrates are biphasic concave downwards (and partially upwards) with a break point at Y = H. The signs and magnitudes of the cross-interaction constant (${\rho}_{XY}$) are strongly dependent upon the nature of substituents, X and Y. The proposed mechanism is a stepwise process with a rate-limiting step change from bond breaking with the weaker electrophiles to bond formation with the stronger eletrophiles. The nonlinear free energy correlations of biphasic concave upward plots for substituent X variations in the nucleophiles are rationalized by a change in the attacking direction of the nucleophile from a backside with less basic pyridines to a frontside attack with more basic pyridines.

• Applied Biological Chemistry
• /
• v.31 no.4
• /
• pp.361-370
• /
• 1988

To investigate the interaction between whey and soybean protein, thermal changes of component proteins were analyzed by column chromatography and gel electrophoresis. In the Sephadex G-200 chromatography of the mixture treated at above $80^{\circ}C$, the amount of low molecular weight proteins and high molecular aggregates were increased. This implicated that dissociation of 1ls globulin into subunits and the formation of soluble aggregates between these subunits and whey proteins that contain thiol and disulfide groups. These interaction between soy proteins and ${\beta}-lactoglobulin$, ${\alpha}-lactalbumin$, and proteose-peptone 3 were confirmed by gel electrophoresis. Bovine serum albumin, Immunoglobulin-G(H), Lactoferrin, 1ls-subunits(basic and acidic), and subunit of 7s globulin were also considered to interact each other depending on the condition of the salt solutions.

• Journal of the Korean Chemical Society
• /
• v.18 no.3
• /
• pp.180-188
• /
• 1974

Adsorption mechanism of alkyl aldehydes, acetaldehyde, acrolein, and crotonaldehyde on cations supported by layer silicates was studied by means of IR spectroscopy and X-ray. An analysis of four characteristic split bands in the region of $1720∼1580㎝^{-1}$ was made. The carbonyl stretching band which shifted about $130㎝^{-1}$ to lower frequencies was observed only for $Ni^{2+}$ and Al^{3+}$ but slightly with $Ca^{2+}$ at high sample temperature and was attributed to >C=O…M complex formation. A sharp band which appeared as a shoulder at 1722 for acetaldehyde and 1690 for acrolein and crotonaldehyde was responsible for the interaction of carbonyl with surface hydroxyl. The second broad band which appeared at about 1710~1660 was responsible for hydrogen bonding between carbonyl oxygen and cationic hydroxyl group. The third band which appeared at about 1640~1660 was attributed to induced >C=C< double bond due to the strong carbonyl interaction. This was supported by the interlamellar spacings obtained by X-ray diffractometry.

• Journal of Integrative Natural Science
• /
• v.8 no.3
• /
• pp.209-213
• /
• 2015

Influenza A virus (H1N1) causes and spreads infectious diseases and becomes a major health threat in humans. Among the subtypes of influenza virus, neuraminidase (NA) plays an important role in viral life cycle and becomes an attractive therapeutic target. Currently two NA inhibitors namely Zanamivir and Oseltamivir are available for treating infectious diseases. Recently five naturally derived polyphenols extracted from Phellinus baumii was reported as inhibitors against NA. Molecular docking is powerful tool in computer aided drug designing which aids in exploring and elucidating the properties of the molecules from their 3D structure. Hence, in the present study, molecular docking was carried out on reported polyphenols isolated from ethanolic extract of fruiting bodies of Phellinus baumii. The objective of this work was to study the interaction and to propose the binding mode of these compounds within the binding site of H1N1 neuraminidase. The results showed these compounds had better binding energy and H-bond interactions with the important active site residues of the receptor which authenticate these compounds contributes to inhibitory activity of neuraminidase to treat influenza infection.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.6
• /
• pp.935-938
• /
• 2005

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to $\alpha-cyano-\beta$-phenylacrylamides (CPA; $YC_6H_4CH=C(CN)CONH_2$) have been investigated in acetonitrile at 25.0 ${^{\circ}C}$. The rate is first order with respect to BA and CPA and no base catalysis is observed. The addition of BA to CPA occurs in a single step in which the addition of BA to $C_{\beta}$ of CPA and proton transfer from BA to $C_{\alpha}$ of CPA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($\rho_X$) and Bronsted ($\beta_X$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the crossinteraction constant, $\rho_XY$ (= −D0.26), is comparable to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($k_H/k_D\;{\gt}$ 1.0) and relatively low ${\Delta}H^{\neq}$ and large negative ${\Delta}S^{\neq}$ values are also consistent with the mechanism proposed.

• Bulletin of the Korean Chemical Society
• /
• v.20 no.10
• /
• pp.1136-1144
• /
• 1999

The collision-induced reaction of gas-phase atomic hydrogen with hydrogen atoms chemisorbed on a silicon (001)-(2×1) surface is studied by use of the classical trajectory approach. The model is based on reaction zone atoms interacting with a finite number of primary system silicon atoms, which then are coupled to the heat bath, i.e., the bulk solid phase. The potential energy of the Hads‥Hgas interaction is the primary driver of the reaction, and in all reactive collisions, there is an efficient flow of energy from this interaction to the Hads-Si bond. All reactive events occur on a subpicosecond scale, following the Eley-Rideal mechanism. These events occur in a localized region around the adatom site on the surface. The reaction probability shows the maximum near 700K as the gas temperature increases, but it is nearly independent of the surface temperature up to 700 K. Over the surface temperature range of 0-700 K and gas temperature range of 300 to 2500 K, the reaction probability lies at about 0.1. The reaction energy available for the product states is small, and most of this energy is carried away by the desorbing H2 in its translational and vibrational motions. The Langevin equation is used to consider energy exchange between the reaction zone and the bulk solid phase.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.1460-1464
• /
• 2014

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.

• Journal of Integrative Natural Science
• /
• v.8 no.1
• /
• pp.30-39
• /
• 2015

The crystal structure of the potential active 2-amino-4-(4-hydroxy-3-methoxyphenyl)-7, 9-dimethyl-5-oxo-4, 5, 6, 7-tetrahydropyrano [2, 3-d] pyrazolo [3, 4-b] pyridine-3-carbonitrile ($C_{21}H_{22}N_5O_6S$) has been determined from single crystal X-ray diffraction data. In the title compound crystallizes in the monoclinic space group P-1 with unit cell dimension a=8.1201(9)${\AA}$, b=12.2684(4)${\AA}$ and c=12.387(2)${\AA}$ [${\alpha}=69.573^{\circ}$, ${\beta}=12.168^{\circ}$ and ${\gamma}=76.060^{\circ}$]. In the structure the pyrazole, pyridine and pyran are almost coplanar each other. The crystal packing is stabilized by intermolecular C-H...O and N-H... O hydrogen bond interaction.