Nucleophilic Substitution Reactions of 1-Halogeno-4-COR-2-nitrobenzenes and 1-Halogeno-6-COR-2-nitrobenzenes with Sodium Benzenethiolate and Piperidine. Can an "Inverted Built-In Solvation" Be Responsible for the Peculiar Activation by an o-Carboxamido Group in S(N)Ar Reactions with an Anionic Nucleophile?
A kinetic study of the title reactions has allowed an interpretation of the higher efficiency of an o-carboxamido group with respect to an o-carbomethoxy group in activating the benzenethiolate-dehalogenation reactions in methanol (k(CONH)()2/k(CO)()2(Me) 2.2-3.0) as due to an interaction between the anionic nucleophile and the hydrogen atoms of the carboxamido group. An inversion of the activating power of the two groups (k(CONH)()2/k(CO)()2(Me) 0.14) in the reactions with the same nucleophile has been observed when they are in a para-position. Moreover, for piperidino-dehalogenation reactions in methanol k(CONH)()2/k(CO)()2(Me) ratios less than unity (0.2-0.6) have been observed independently of the position (ortho or para) of the carboxamido and carbomethoxy groups with respect to the reaction center.
Arnone
Caterina
C
Dipartimento di Chimica Organica 'A. Mangini', Università di Bologna, Via San Donato 15, 40127 Bologna, Italy, and Dipartimento di Chimica Organica, Università di Palermo, Via Archirafi 20, 90123 Palermo, Italy.
Consiglio
Giovanni
G
Frenna
Vincenzo
V
Spinelli
Domenico
D