• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1945-1950
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• 2011

The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.

• Journal of Environmental Science International
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• v.18 no.9
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• pp.953-959
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• 2009

A practical and efficient disposal method for chemical dechlorination of PCBs (polychlorinated biphenyls) in transformer oil was evaluated. The transformer oil containing PCBs was treated by the PEG 600 (polyethylene glycol 600) and potassium hydroxide (KOH) along with different reaction temperatures(25, 50, 100 and $150^{\circ}C$) and times(30, 60, 240 and 480 min). The best disposal efficiency of PCBs in transformer oil was attained under the experimental conditions of PEG 600 (2.5 w/w%)/KOH (2.5 w/w%)/$150^{\circ}C$/4 hrs, showing completely removal of all PCBs containing 3-9 chlorines on two rings of biphenyl. In studying the reaction of PEG/KOH with PCBs, it confirmed that the process led to less chlorinated PCBs through a stepwise process with the successive elimination of chlorines.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2130-2134
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate (7) with a series of cyclic secondary amines in MeCN. The plots of $k_{obsd}$ vs. [amine] curve upward for the reactions with weakly basic amines (e.g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e.g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e.g., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i.e., the deprotonation process to yield $T^-$ from $T^{\pm}$ by a second amine molecule) is absent. The Br${\o}$nsted-type plots for $Kk_2$ and $Kk_3$ (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with ${\beta}_{nuc}$ = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2443-2447
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate (7) and 4-nitrophenyl isonicotinate (8) with a series of cyclic secondary amines in $H_2O$ containing 20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plots for the reactions of 7 and 8 are linear with ${\beta}_{nuc}=0.90$ and 0.92, respectively, indicating that the reactions proceed through a stepwise mechanism with expulsion of the leaving group occurring in the rate-determining step. Comparison of the reactivity of 7 and 8 with that of 4-nitrophenyl benzoate (2a) and 4-nitrophenyl picolinate (6) has revealed that their reactivity toward the amines increases in the order 2a < 7 < 8 < 6, although the reactions of these substrates proceed through the same mechanism. Factors that control reactivity and reaction mechanism have been discussed in detail (e.g., inductive and field effects, H-bonding interaction, solvent effect, etc.).

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.767-771
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• 2008

Second-order rate constants have been measured spectrophotometrically for the Michael-type reaction of 1-(Xsubstituted phenyl)-2-propyn-1-ones (2a-f) with amines in $H_2O$ at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. A linear Brønsted-type plot is obtained with ${\beta}_{nuc}$ = 0.25 ${\pm}$ 0.02, a typical $\beta_{nuc}$ value for reactions which proceed through a stepwise mechanism with attack of amine on the electrophilic center being the rate-determining step. Secondary alicyclic amines are found to be more reactive than isobasic primary amines. The Hammett plot for the reactions of 2a-f with morpholine is not linear, i.e., the substrate with a strong electron-donating group (e.g., 4-MeO) exhibits a negative deviation from the Hammett plot. However, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.62 and r = 0.82. Thus, it has been proposed that the nonlinear Hammett plot is not due to a change in the ra te-determining step but due to ground-state stabilization through resonance interactions.

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3587-3591
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• 2011

The reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-benzylamines are kinetically investigated in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}x$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots are biphasic concave downwards for substituent X variations in the nucleophiles with a break point at X = H. The signs of the cross-interaction constants (${\rho}xz$) are positive for both the strongly and weakly basic nucleophiles. Considerably great magnitude of ${\rho}xz$ (= 6.56) value is observed with the weakly basic nucleophiles, while ${\rho}xz$ = 0.91 with the strongly basic nucleophiles. Proposed reaction mechanism is a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving a backside nucleophilic attack with the strongly basic nucleophiles and a frontside attack with the weakly basic nucleophiles. The kinetic results are compared with those of the benzylaminolysis of O,O-diphenyl Z-S-aryl phosphorothioates.

• Korean Journal of Applied Biomechanics
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• v.34 no.1
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• pp.1-8
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• 2024

Objective: The aim of this study was to identify the biomechanical determination factor for improving club head speed during the driver swing in male golf players. Method: Twenty-seven golf players were participated in this study. Eight motion capture cameras (250 Hz) and two force plates (2,000 Hz) were used to collect peak angular velocity and ground reaction force data. It was performed stepwise multiple linear regression analysis and alpha set at .05. Results: The peak plantar flexion angular velocity of the left ankle joint and the peak adduction angular velocity of the right shoulder joint were statistically significant. The peak plantar flexion angular velocity of the left ankle joint and the peak adduction angular velocity of the right shoulder during downswing. Conclusion: It is suggested that applying body conditioning training aimed at improving related body functions to increase maximum plantar flexion angular velocity in the left ankle joint will be effective in improving club head speed.

• KSBB Journal
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• v.26 no.4
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• pp.300-304
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• 2011

Phytases are hydrolytic enzymes that catalyze the sequential hydrolysis of phytic acid (myo-inositol-1,2,3,4,5,6-hexakisphosphate) to myo-inositols with lower numbers of phosphate groups. Two types of phytases have been identified which initiate hydrolysis of the phytic acid at either the 3- or 6- position of the inositol ring. In the present investigation, a mathematical model was proposed and computed to estimate maximum enzyme reaction rate constants which fit the experimental data obtained by other authors. Although the data points were scattered to some extent, good agreement was found between the model and the experiment data. It appears that the maximum rate constants of removal of the first, second, and third phosphate groups were not equal. Also there was neither a steady trend upward or downward in the rate constants with the stepwise hydrolysis reactions.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1042-1046
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• 2012

The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of diethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit the two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with rate-limiting expulsion of the isothiocyanate leaving group from a trigonal bipyramidal pentacoordinated intermediate. The relatively large ${\beta}_x$ values with more basic and less basic pyridines imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2797-2802
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• 2014

Nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed for 8 based on the negative ${\rho}_{XY}$ (= -0.23) value, while a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed for 10 based on the positive ${\rho}_{XY}$ (= +0.68) value. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are 0.89-1.28 and 0.62-1.20 with 8 and 10, respectively. Primary normal and secondary inverse DKIEs are rationalized by a frontside attack involving hydrogen bonded, four-center-type transition state and backside attack involving in-line-type transition state, respectively.