152814-26-1Relevant articles and documents
CROSSED EFFECT OF THE POLAR CHARACTERISTICS OF THE MEDIUM AND THE STRUCTURE OF THE SUBSTRATE IN THE REACTIONS OF AROYL CHLORIDES WITH N-METHYLANILINES
Shpan'ko, I. V.,Litvinenko, L. M.,Goncharov, A. N.,Korzhilova, O. I.
, p. 847 - 853 (2007/10/02)
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.