• Bulletin of the Korean Chemical Society
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• v.22 no.6
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• pp.633-634
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• 2001

• Bulletin of the Korean Chemical Society
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• v.16 no.8
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• pp.760-763
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• 1995

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.413-418
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• 1989

The rates for the reaction of substituted 2-phenylethyl tosylates with substituted pyridines were measured in acetonitrile and that of 2-PNS with substituted pyridines were investigated in both acetonitrile and methanol. The substitutent effect was accelerated by an electron-donating substituent on both substrate and nucleophile. Results showed that More O'Ferrall and quantum mechanical model of predicting transition state structure suggest the reaction proceeds via an $S_N2$ mechanism, in which bond-breaking is more advanced than bond-formation. Transition state variation predicted with the quantum mechanical model is consistent with the experimental results, whereas the predictions provided by the More O'Ferrall plots is found to be inconsistent in leaving group. In the reaction of 2-PNS, the rate constants in acetonitrile were larger than that in methanol.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.433-435
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• 1984

• Journal of the Korean Chemical Society
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• v.38 no.12
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• pp.915-920
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• 1994

The Menschutkin type reactions of substituted (Z)-benzyl (X)-arenesulfonates with substituted(Y)-pyridines were studied by the electroconductometric method in acetonitrile at $35\circC$. Hammett $\rho$ values were calculated by the second order rate constants for the reaction of substituted (Z)-benzyl (X)-arenesulfonates with substituted (Y)-pyridines. The negative $\rho_Y$ values meant positive charge development on the nitrogen of pyridine at transition state owing to the charge development on the oxygen atom of benzenesulfonate. And the negative $\rho_Z$ values meant positive charge development on the benzylic carbon. Application of the multi-Hammett interaction,│$\rho_YZ$│ > │$\rho_XY$│ > │$\rho_ZX$│, the Menschutkin type reaction of substituted benzyl arenesulfonates with substituted pyridines was shown to be dissociative $S_N2$ mechanism.

• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.643-649
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• 1995

The Menschutkin type reactions of substituted(Z)-benzyl systems with substituted(Y)-pyridines and N,N-dimethyl aniline have been studied by the electro-conductometric method in acetonitrile at 35$^{\circ}C$ and 50$^{\circ}C$. On the plot of $k_{obs}$ versus concentrations of nucleophile under pseudo-first order conditions, 3,$4-(CH_3/O)_2$-benzyl bromide and $4-CH_3O$-benzyl bromide were a positive intercept at zero concentration of nucleophile. The $k_1$ value for each compound was invariant with the different nucleoephile. However, $4-CH_3-$ and other electron withdrawing substituents of benzyl bromides did not show the positive intercept. These results are suggested that the reactions have been proceeding simultaneously and independently for the activated benzyl bromides via direct bimolecular and intimate ion pair intermediate.