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Anilinolysis of Picryl Benzoate Derivatives in Methanol: Reactivity, Regioselectivity, Kinetics, and Mechanism
Author(s) -
Ibrahim Mahmoud F.,
ElAtawy Mohamed A.,
ElSadany Samir K.,
Hamed Ezzat A.
Publication year - 2013
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20779
Subject(s) - chemistry , regioselectivity , bond cleavage , reaction rate constant , aryl , cleavage (geology) , reactivity (psychology) , aniline , medicinal chemistry , oxygen , nucleophilic aromatic substitution , stereochemistry , kinetics , photochemistry , organic chemistry , nucleophilic substitution , catalysis , medicine , physics , geotechnical engineering , alternative medicine , pathology , quantum mechanics , fracture (geology) , engineering , alkyl
The reaction of picryl benzoate derivatives 1a–g with aniline in methanol proceeds through COO and ArO bond cleavage pathways. Furthermore, the reactivity of these esters toward anilinolysis is correlated to the energy gap between highest occupied molecular orbital aniline and lowest unoccupied molecular orbital of each ester. The regioselectivity of acyloxygen versus aryloxygen cleavage is also discussed. The overall rate constants k tot split into k COO (the rate constant of acyl‐oxygen cleavage) and k ArO (rate constant of aryl‐oxygen cleavage). The COO bond cleavage advances through a stepwise mechanism in which the formation of the tetrahedral intermediate is the rate‐determining step. The ArO bond cleavage continues through a S N Ar mechanism in which the departure of the leaving group from the Meisenheimer complex occurs rapidly after its formation in the rate‐determining step.