• Archives of Pharmacal Research
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• v.14 no.4
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• pp.285-289
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• 1991

A convenient spectrophotometric method was examined for the determination of amantadine sulfate (AMTS) which has no UV-VIS chromopohores. AMTS was ion-paired quantitatively with methyl orange (MO) at $70^{\circ}C$ for 30 min. The ion-paired complex was extracted with dichloromethane and the absorbance was measured at 421.5 nm. A linear relationship was observed in the range of $2.5{\times}10^{-7}\;M$ to $3.75{\times}10^{-6}\;M$ and the correlation coefficient was 0.999 (n=3). This assay method was applied to the quantification of AMTS in commercial tablet form with good recovery and high precision.

• YAKHAK HOEJI
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• v.37 no.3
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• pp.209-215
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• 1993

Basic drugs could be extracted as ion-paired complexes with Lumogallion, Superchrome Garnet Y and their alkyl derivatives from aqueous acid solution, and then determined fluoro-metrically after addition of aluminum ion. The analysis was carried out as follows; To a 1 ml portion of basic drugs (10$^{-9}$~2$\times$0$^{-8}$mole/ml), 1ml of 0.01w/v% fluorescent reagent solution, and 10ml of dichloroethane are added. The mixture is stirred for 1 minute. After standing for a few minutes, the dichloroethane layer is transfered to 1 ml of 0.1w/v% Al(NO$_{3}$)$_{3}$ ethanol solution. After mixing, and standing for 30 minutes at room temperature, the fluorescence intensity is measured with each maximum excitation and emission wavelength. The reagent blank is run through the whole procedure. From the degree of enhancement of fluorescence intensity, hexyl and dodecyl lumogallion and Superchrome Garnet Y were judged to be the useful one of fluorescent reagent for basic drugs analysis.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.117-121
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• 2008

Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 5-nitro-8-quinolyl benzoate (5) with alkali metal ethoxides, EtO?M+ (M+ = Li+, Na+ and K+) in anhydrous ethanol (EtOH) at 25.0 0.1 C. The plots of kobsd vs. [EtO?M+] exhibit upward curvatures, while the corresponding plots for the reactions of 5 with EtO?Na+ and EtO?K+ in the presence of complexing agents, 15-crown-5-ether and 18-crown-6-ether are linear with rate retardation. The reactions of 5 with EtO?Na+ and EtO?Li+ result in significant rate enhancements on additions of Na+ClO4, indicating that the M+ ions behave as a catalyst. The dissociated EtO and ion-paired EtOM+ have been proposed to react with 5. The second-order rate constants for the reactions with EtO (kEtO) and EtOM+ (kEtOM+) have been calculated from ion-pairing treatments. The kEtO and kEtOM+ values decrease in the order kEtONa+ > kEtOK+ > kEtOLi+ > kEtO, indicating that ion-paired EtOM+ species are more reactive than the dissociated EtO ion, and Na+ ion exhibits the largest catalytic effect. The M+ ions in this study form stronger complex with the transition state than with the ground state. Coordination of the M+ ions with the O and N atoms in the leaving group of 5 has been suggested to be responsible for the catalytic effect shown by the alkali metal ions in this study.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3543-3548
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• 2010

A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.