• Bulletin of the Korean Chemical Society
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• 제32권12호
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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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• 제32권10호
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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.