• 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.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4304-4308
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• 2011

Kinetic studies of the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out 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 for substituent X variations in the nucleophiles are discrete with a break region between 4-Me and H, while the Hammett plots (log $k_2$ vs ${\sigma}_Z$) for substituent Z variations in the leaving groups are linear. The sign of the cross-interaction constant (${\rho}_{XZ}$) is positive for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ (= 2.54) value is observed with the weakly basic nucleophiles compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = 0.17). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a stepwise with a rate-limiting leaving group expulsion from the intermediate involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles.

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3743-3747
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• 2011

Kinetic studies on the reactions of Y-S-aryl phenyl phosphonochloridothioates with X-pyridines have been carried out in MeCN at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H. The Hammett plots for substituent Y variations in the substrates are biphasic concave upwards with a break point at Y = H, and the sign of ${\rho}_Y$ is changed from unusual negative (${\rho}_Y$ < 0) with the weaker electrophiles to positive (${\rho}_Y$ > 0) with the stronger electrophiles. The stepwise mechanism is proposed on the basis of the ${\rho}_X$, ${\beta}_X$, and ${\rho}_{XY}$ values as follows: a ratelimiting leaving group departure from the intermediate involving a frontside attack and product-like TS for the stronger nucleophiles and weaker electrophiles; a rate-limiting leaving group departure from the intermediate involving a backside attack and product-like TS for the weaker nucleophiles and electrophiles; a rate-limiting bond formation involving a frontside attack for the stronger nucleophiles and electrophiles; a rate-limiting bond formation involving a backside attack for the weaker nucleophiles and stronger electrophiles. The substituent effects of X and Y on the pyridinolysis mechanisms of $R_1R_2P$(=S)Cl-type substrates are discussed.

• Bulletin of the Korean Chemical Society
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• v.25 no.12
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• pp.1924-1928
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• 2004

Allylations of N-benzyl and N-methyl cyclic imides were accomplished successfully under mild Barbier type conditions using zinc metal, allyl bromide and catalytic amount of $PbBr_2$. Subsequent coupling reactions with some carbon nucleophiles afforded 1,2- and 1,4-addition products in moderate to high yields.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.632-636
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• 1992

Second-order rate constants have been determined spectrophotometrically for nucleophilic substitution reactions of p-nitrophenyl benzoate with various anionic nucleophiles including 6 ${\alpha}$ -effect nucleophiles. The logarithmic second-order rate constants for the aryloxides give a good Bronsted correlation with the respective basicity while the ones for p-chlorothiophenoxide and hydroxide exhibit significantly positive and negative deviations, respectivity, from the Bronsted linear line. The deviations are attributed to a solvation effect rather than a change in the reaction mechanism. The ${\alpha}$-effect nucleophiles except highly basic ones demonstrate significantly higher nucleophilicity (the ${\alpha}$ -effect) than would be predicted from the respective basicity. The effect of solvation and polarizability appears to be important for the ${\alpha}$-effect as well as for the reaction rate.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.789-791
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• 2002

• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.695-696
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• 2014

• Bulletin of the Korean Chemical Society
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• v.17 no.3
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• pp.234-238
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• 1996

Second-order rate constants have been measured spectrophotometrically for the reaction of p-nitrophenyl acetate (PNPA) with morpholine, piperazine and piperidine in MeCN-H2O mixtures of varying compositions. The rate of the present aminolysis decreases upon additions of MeCN into H2O up to near 30-40 mole % MeCN and remains nearly constant upon further additions of MeCN. The reaction of PNPA with anionic nucleophiles, such as HO-, p-chlorophenoxide and butane-2,3-dione monoximate, has also exhibited two distinguishable reactivity zones. However, the reactivity trend for the anionic nucleophiles is quite different from the one obtained for the amine system, e.g. an initial rate decrease in the H2O-rich region followed by an increasing rate trend upon further additions of MeCN in the MeCN-rich region. The rate behaviors shown by the amine system in the MeCN-rich and by the anionic system in the H2O-rich region are unexpected based on the Hughes-Ingold rules. The present unusual rate trends have been attributed to changes in the solvent structure and pKa of the nucleophiles upon the addition of MeCN into H2O. The effect of solvent appears to be more significant for the TS than the GS, and the TS structure is considered to become tighter in the higher MeCN concentration.

• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1625-1629
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• 2011

Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2286-2290
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• 2013

Ring opening reactions of epoxides with oxygen nucleophiles catalyzed by a variety of quaternary onium salt, such as ammonium or phosphonium salt were explored. The results showed that tetrabutylphosphonium bromide (TBPB) among salts serves as the most efficient catalyst for this process and that expoxide ring opening reactions with a variety of oxygen nucleophiles including carboxyic acid and phenol, promoted using this salt, lead to generate readily purifiable products in excellent yields.