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Reactions of Azolium cations. II [1]. Regioselective N2 alkylation of 5‐aryltetrazoles with isopropyl alcohol in sulfuric acid media: Effect of electronic properties of aryl substituents on the reaction rate
Author(s) -
Koren A. O.,
Gaponik P. N.,
Ostrovskii V. A.
Publication year - 1995
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.550270908
Subject(s) - chemistry , sulfuric acid , reaction rate constant , substituent , regioselectivity , alkylation , hammett equation , isopropyl alcohol , alcohol , isopropyl , medicinal chemistry , aryl , mndo , computational chemistry , organic chemistry , alkyl , kinetics , molecule , catalysis , physics , quantum mechanics
Abstract Kinetics of regioselective N2 alkylation of a series of 5‐(R‐phenyl)tetrazoles with isopropyl alcohol has been studied in 88.2, 94.3, and 98.3% (w/w) sulfuric acid at 25°. The true rate constants were evaluated, logarithms of which were found to correlate with σ° constants of phenyl substituents as log k = −0.488 σ° − 0.417. Small value of Hammett constant ρ is evidence of a considerable isolation of the reaction center from the influence of the substituent at position C5 of the heteroring. This conclusion is confirmed by results of MNDO quantum chemical calculations of a series of 5‐substituted tetrazolium cations. A correlation between logarithms of the true rate constants and the calculated net effective charges on atoms N2(N3) for 5‐(R‐phenyl)tetrazolium cations has been revealed. © 1995 John Wiley & Sons, Inc.