- EFFECT OF STRUCTURE OF REAGENTS AND TEMPERATURE IN THE REACTIONS OF AROYL CHLORIDES WITH N-METHYLARYLAMINES IN BENZENE
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The kinetics of the reactions of aroyl chlorides with N-methylarylamines in benzene were studied with crossed variation in the structures of the reagents.The attainment of the isoparametric point with respect to the structure of the N-methylarylamine was demonstrated by crossed correlation.The energy parameters for the reactions of benzoyl chloride with N-methylarylamines are 10percent lower than those obtained for primary arylamines.The higher reactivity of the N-methylarylamines compared with the corresponding primary arylamines is due to the resonance stabilization of the transition state.
- Titskii, G. D.
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p. 1714 - 1718
(2007/10/02)
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- CROSSED EFFECT OF THE POLAR CHARACTERISTICS OF THE MEDIUM AND THE STRUCTURE OF THE SUBSTRATE IN THE REACTIONS OF AROYL CHLORIDES WITH N-METHYLANILINES
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A kinetic investigation was undertaken into the reactions of aroyl chlorides with 3-bromo- and 3-nitro-N-methylanilines in chlorobenzene, nitrobenzene, cyclohexane, and binary mixtures of chlorobenzene with nitrobenzene and cyclohexane at 25 deg C.The second-order rate constants of the reaction involving N-methyl-3-bromoaniline were treated by means of the Kirkwood, Hammet, and crossed structure-medium correlation equations.It was found that the correlations according to the Kirkwood and Hammet equation can be linear or broken, depending on the structure of the reagents and the characteristics of the medium.The presence of bends on the correlation curves is due to the appearance on the reaction coordinate in low-polarity media of a cyclic transition state, the formation of which is promoted by increase in the electron-withdrawing characteristics of the substituents in the benzene ring of both the amine and the aroyl chloride.The attainment of an isoparametric point with respect to the structure of the substrate in the region corresponding to the realization of the cyclic transition state was demonstrated by crossed correlation.
- Shpan'ko, I. V.,Litvinenko, L. M.,Goncharov, A. N.,Korzhilova, O. I.
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p. 847 - 853
(2007/10/02)
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