50892-00-7Relevant academic research and scientific papers
VARIATION OF TRANSITION STATE IN REACTIONS OF BENZENSULFONYL CHLORIDES WITH ANILINES IN MeOH-MeCN SOLVENTS
Lee, Ikchoon,Koo, In Sun
, p. 1803 - 1808 (1983)
Kinetic studies of nucleophilic substitution reactions of substituted benzenesulfonyl chlorides with anilines were conducted at 35 deg C in a range of methanol-acetonitril solvent mixtures.Results showed that (i) the magnitudes of ρN and β associated with a change of substituent in the nucleophile are large and indicate a relatively advanced bond-formation in the transition state, (ii) maximum size of ρN, ρS and β at the solvent composition of the maximum ionizing power, together with a positive cross-interaction coefficient, suggest SN2 transition state of a "synchronous push-pull" type, and (iii) the potential energy surface model is unstable to predict the transition state variation to a more product-like transition state, where bond formation is much more progressed and bond-breaking is slightly more advanced, upon changing the solvent to a more ionizing one enhancing leaving ability.In this respect the quantum mechanical model is superior to the potential energy surface model.
