Reactions of Azolium Cations. II. Regioselective N2 Alkylation of 5-Aryltetrazoles with Isopropyl Alcohol in Sulfuric Acid Media: Effect of Electronic Properties of Aryl Substituents on the Reaction Rate

Article abstract of DOI:10.1002/kin.550270908

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 98.3percent (w/w) sulfuric acid at 25 deg.The true rate constants were evaluated, logarithms of which were found to correlate with ?⁰ constants of phenyl substituents as log k = -0.488?⁰ - 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.