• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.122-126
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• 1994

Corrosion of brass coated steel cords in the acetonitrile solution of sulfenamide derivatives, N-Cyclohexylbenzothiazole-2-sulfenamide (CBTS), N,N'-Dicyclohexylbenzothiazole-2-sulfenamide (DCBS), N-tert-Butylbenzothiazole-2-sulfenamide (TBBS), N-tert-Amylbenzothiazole-2-sulfenamide (TABS), and N-Oxydiethylbenzothiazole-2-sulfenamide (OBTS) was investigated by potentiostatic anodic and cathodic polarization (Tafel plot), DC polarization resistance, and AC impedance measurements. The corrosion current densities and rates are 1.236 ${\mu}A /cm^2$ and 0.655 MPY for CBTS; 1.881 ${\mu}A/cm^2$ and 0.988 MPY for DCBS; 2.367 ${\mu}A/cm^2$ and 1.257 MPY for TBBS; 3.398 ${\mu}A /cm^2$ and 1.809 MPY for TABS, respectively. OBTS among derivatives under study shows the lowest corrosion density (0.546 ${\mu}A /cm^2$) and the slowest corrosion rate (0.288 MPY). Also, the charge transfer resistances and the double layer capacitances are 275.21 $k{\Omega}{\cdot}cm^2$ and 7.0 ${\mu}F{cdot}cm^{-2}$ for CBTS; 14.24 ${\mu}F{\cdot}cm^2$ and 26 ${\mu}F{\cdot}cm^{-2}$ for DCBS; 54.15 $k{\Omega}{\cdot}cm^2$ and 26 ${\mu}F{\cdot}cm^{-2}$ for TBBS; 0.96$k{\Omega}{\cdot}cm^2$ and 83 ${\mu}F{\cdot}cm^{-2}$ for TABS, respectively. The weaker the electron donating inductive effect of derivatives is and the smaller the effect of steric hindrance is, the more the corrosion of brass coated steel cords in the acetonitrile solution of sulfenamide derivatives is prevented. The above results agree with that observed in the field of tire industry.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1037-1041
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• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.733-738
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• 2006

Nucleophilic addition reactions of p-substitutedbenzylamines $(XC _6H_4CH _2NH _2)$ to $\alpha$-phenyl-$\beta$-thiophenyl-acrylonitriles ($YC _4SH _2CH=C(CN)C_6H_4$Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 ${^{\circ}C}$. The reactions take place in single step in which the $C_\beta$ -N bond formation and proton transfer to $C_\alpha$ of $\alpha$-phenyl-$\beta$-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative $\rho$x and large positive $\rho$Y' values and also large magnitude of $\rho$X, (ii) the negative sign and large magnitude of the cross-interaction constants ($\rho$XY), (iii) the normal kinetic isotope effects ($k_H/k_D$ > 1.0), and (iv) relatively low $\Delta H ^\neq$ and large negative $\Delta S ^\neq$ values.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1670-1674
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• 2007

Addition reactions of anilines (XC6H4NH2) to β-nitrostilbene (YC6H4CH=C(NO2)C6H4Y') have been investigated in acetonitrile at 30.0 oC. The magnitude of βX values (=0.11-0.34) indicates relatively earlier transition state for additions with anilines than with benzylamines. The signs of ρY and ρY' are positive with Δρ = ρY?ρY' = 0.04, demonstrating a TS imbalance with a negative charge development on the Cβ in the TS. The signs of cross-interaction constants ρXY (<0), ρXY' (<0) and ρYY' (>0) are consistent with bond forming and breaking processes. The relatively weak normal kinetic isotope effects involving deutarated nucleophiles, kH/kD>1, suggest an early, hydrogen-bonded, 4-member cyclic TS.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.221-224
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• 2002

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to ethyl-${\alpha}$-cyanocinnamates (ECC;$YC_6H_4CH$=C(CN)COOEt) have been investigated in acetonitrile at $30.0^{\circ}C$. The rate is first order with respect to BA and ECC. The rate is slower than that expected from the additive effect of ${\sigma}^-$ or $R^-$ for the activating groups (CN and COOEt). Natural. bond orbital ${\pi}^{\ast}_{c=c}$ calculations show that the contribution of COOEt group may not be fully effective despite the coplanar molecular structure. The selectivity parameters including the cross-interaction constant (${\rho}_{xy}$ = -0.22) indicate that the addition occurs in a single step. The kinetic isotope effects ($k_H/k_D$=2.5-2.8) involving deuterated BA ($XC_6H_4CH_2ND_2$) nucleophiles and activation parameters (${\Delta}H^{\neq}=4{\sim}6\;kcal\;mol^{-1};{\Delta}S^{\neq}=-45{\sim}-52\;e.u.$) suggest a cyclic transition state in which N-$C_{\alpha}$ and H-$C_{\beta}$ bonds are formed concurrently.

• Korean Journal of Veterinary Research
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• v.48 no.1
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• pp.33-38
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• 2008

In veterinary medicine amitraz has been used as an insecticide to eliminates mites, lice, and ticks in dogs, cats, goats, swine and cattle. The objective of present study was to developed an analytical method using one-step extraction and determination of the amitraz in veterinary drugs by liquid chromatography (LC). The amitraz was analyzed by LC equipped with Waters XTerra RP18 ($4.8{\times}250mm;\;5{\mu}m;\;Waters,\;USA$) analytical column, using 75% acetonitrile (acetonitrile/D.W; 75/25) at 1.0 ml/ min. The UV-VIS detection of amitraz was made at 290 nm. Calibration graphs were linear with very good correlation coefficients ($r^2>0.9999$) from $80{\sim}120{\mu}g/ml$. The limit of detection was $0.09{\mu}g/ml $ and limit of quantification was $0.27{\mu}g/ml $. The method showed good intra-day precision (CV 0.05~0.09%) and inter-day precision (CV 0.06~0.18%).

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1939-1944
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• 2011

The nucleophilic substitution reactions of bis(Y-aryl) chlorophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 35.0 $^{\circ}C$. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorophosphates (2). The substrate 1 has one more identical substituent Y compared to substrate 2. The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of cross-interaction constant (CIC) from negative ${\rho}_{XY}$ = -1.31 (2) to positive ${\rho}_{XY}$ = +1.91 (1), indicating the change of reaction mechanism from a concerted $S_N2$ (2) to a stepwise mechanism with a rate-limiting leaving group departure from the intermediate (1). The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines ($XC_6H_4ND_2$) show secondary inverse, $k_H/k_D$ = 0.61-0.87. The DKIEs invariably increase as substituent X changes from electron-donating to electron-withdrawing, while invariably decrease as substituent Y changes from electron-donating to electron-withdrawing. A stepwise mechanism with a rate-limiting bond breaking involving a predominant backside attack is proposed on the basis of positive sign of ${\rho}_{XY}$ and secondary inverse DKIEs.

• Bulletin of the Korean Chemical Society
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• v.24 no.2
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• pp.193-196
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• 2003

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)$ to benzylidene Meldrum's acids (BMA; $YC_6H_4CH=C(COO)_2C(CH_3)_2$) have been investigated in acetonitrile at 20.0 ℃. The rates of addition are greatly enhanced due to the abnormally high acidity of Meldrum's acid. The magnitudes of the Hammett $({\rho}_X\;and\;{\rho}_Y)$ and Bronsted $({\rho}_X$)$ coefficients are rather small suggesting an early transition state. The sign and magnitude of the cross-interaction constant, ${\rho}_{XY}$ (= -0.33), and kinetic isotope effects $(k_H/k_D\;{\stackrel}{~}{=}\;1.5-1.7)$ involving deuterated benzylamine nucleophilies $(XC_6H_4CH_2ND_2)$ are indicative of hydrogen-bonded cyclic transition state. The activation parameters, ${\Delta}H^{\neq}\;{\stackrel}{~}{=}\;4\;kcal\;mol^{-1}\;and\;{\Delta}S^{\neq}\;{\stackrel}{~}{=}\;-37\;e.u.$, are also in line with the proposed mechanism.

• Proceedings of the Ginseng society Conference
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• 1980.09a
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• pp.59-69
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• 1980

A new HPLC-method for separation and quantitative determination of ginsenosides in Panax ginseng, Panax quinquefolium and in pharmaceutical drug preparations is elaborated. A reversed-phase-system with ${\mu}Bondapak\;C_{18}$ column (3.9 mm $I.D.{\times}30\;cm$) using acetonitrile-water (30:70) 2 ml/min and acetonitrile-water (18:82) 4 ml/min is suitable for the base-line separation of $Rb_1,\;Rb_2,\;Rc,\;Rd,\;Rf,\;Rg_2,\;respectively\;Re,\;Rg_1$ in 30 minutes. The ginsenosides are directly detected at 203 nm (without derivatization) with the LC-55 or LC-75 spectrophotometer (Perkin-Elmer) at $100\%$ transmission. Detection limit is 300 ng at a signal-to-noise ratio of 10:1. The ginsenosides-peak identification is carried out with HPTLC (high performance thin layer chromatography), with MIR-IR (multiple internal reflection-IR-spectros-copy) and with FD-MS (field desorption mass spectrometry). The calibration curve of each ginsenoside has a correlation coefficient very near to 1. Relative standard deviation for quantitative determinations depends upon the amount of ginsenosides and is approximately 1\%$ for ginsenoside contents of 1\%$. This method is adaptable for routine analysis in quality control laboratories.

• Bulletin of the Korean Chemical Society
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• v.19 no.12
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• pp.1334-1336
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• 1998

Kinetic studies are carried out on the reactions of 2-chloro-2-propen-1-yl arenesulfonates with anilines and N,N-dimethylanilines in acetonitrilile at 45.0 ℃. The 2-chloro substituent is found to deactive the allyl moiety with considerable decrease in the rates. The sign and magnitude of the cross-interaction constant (ρxz 0.3) and the inverse secondary kinetic isotope effect (kH/kD 0.92) support an SN2 mechanism with a relatively tight transition state. The possibility of an SN2' mechanism can be safely precluded based on the ρxz values observed.