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Structure‐reactivity relationship of benzyl benzenesulfonates. Part 3. Prediction of reaction mechanism by the use of correlation interaction coefficients
Author(s) -
Yoh SooDong,
Cheong DukYoung
Publication year - 1996
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/(sici)1099-1395(199610)9:10<701::aid-poc832>3.0.co;2-q
Subject(s) - chemistry , sn2 reaction , nucleophile , reactivity (psychology) , computational chemistry , sign (mathematics) , benzene , nucleophilic substitution , medicinal chemistry , reaction rate constant , stereochemistry , organic chemistry , kinetics , catalysis , medicine , alternative medicine , pathology , mathematical analysis , physics , mathematics , quantum mechanics
Nucleophilic substitution reactions of (Z)‐benzyl (X)‐benzene sulfonates with (Y)‐pyridines were investigated in acetone at 35°C. The magnitudes of the Hammett reaction constants ρ X , ρ Y and ρ Z indicate that a stronger nucleophile leads a lesser degree of bond breaking and a better leaving group is accompanied by a lesser degree of bond formation. The magnitude of interaction term, ρ ij , can be used to determine the structure of the transition state (TS) for the S N reaction. In particular, the comparison of ρ XZ with ρ YZ and the sign of ρ Z can predict that this reaction series proceed via dissociative S N 2 process. This result also accords with the treatment of the MOFJ diagram. The sign of the product ρ XZ ρ YZ can predict the movement of the TS.