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Cross interaction constants as a measure of the transition state structure (part III). Mechanism of reactions between 1‐phenylethyl benzenesulfonates with N,N‐dimethylanilines
Author(s) -
Lee Ikchoon,
Kim Hyung Yoon,
Lee Hai Whang,
Kim In Chul
Publication year - 1989
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610020105
Subject(s) - chemistry , nucleophile , leaving group , reactivity (psychology) , hydrogen bond , methanol , medicinal chemistry , selectivity , nucleophilic substitution , photochemistry , computational chemistry , stereochemistry , catalysis , organic chemistry , molecule , medicine , alternative medicine , pathology
The kinetics and mechanisms of the reactions between 1‐phenylethyl benzenesulfonates (1‐PEB) with N,N‐dimethylanilines are investigated in methanol at 35·0°C. Reactivity and selectivity trends were found to be similar to those for the reactions of 1‐PEB with anilines, but the magnitudes of cross interaction constants, ρXZ, between substituents X in the nucleophile and Z in the leaving group were substantially smaller indicating no hydrogen‐bond bypass bridge formation in the transition state. However, the magnitude of ρXZ suggested a direct electrostatic interaction between the reaction centers in the nucleophile and leaving group in the frontside nucleophilic attack with a loose transition state structure.