NDLI: Nucleophilicities and Lewis basicities of imidazoles, benzimidazoles, and benzotriazoles

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Organic & Biomolecular Chemistry Vol - 8 Issue - 7

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Nucleophilicities and Lewis basicities of imidazoles, benzimidazoles, and benzotriazoles

Content Provider	Royal Society of Chemistry (RSC)
Author	Mayr, Herbert Baidya, Mahiuddin Brotzel, Frank
Copyright Year	2010
Abstract	The kinetics of the reactions of some imidazoles, benzimidazoles and benzotriazoles with benzhydrylium ions (diarylcarbenium ions) have been studied photometrically in DMSO, acetonitrile, and aqueous solution at 20 °C. The resulting second-order rate constants have been used to determine the nucleophile-specific parameters N and s of these azoles according to the linear-free-energy relationship log k (20 °C) = s(N + E). With N = 11.47 (imidazole in acetonitrile), N = 10.50 (benzimidazole in DMSO), and N = 7.69 (benzotriazole in acetonitrile) these azoles are significantly less nucleophilic than previously characterized amines, such as DMAP (N = 14.95 in acetonitrile) and DABCO (N = 18.80 in acetonitrile). For some reactions of the 1-methyl substituted azoles with benzhydrylium ions equilibrium constants have been measured, which render a comparison of the Lewis basicities of these compounds. Substitution of the rate and equilibrium constants of these reactions into the Marcus equation yields the corresponding intrinsic barriers ΔG0≠. From the ranking of ΔG0≠ (imidazoles > pyridines > 1-azabicyclooctanes) one can derive that the reorganization energies for the reactions of imidazoles with electrophiles are significantly higher than those for the other amines and that imidazoles are less nucleophilic than pyridines and 1-azabicyclooctanes of comparable basicity.
Starting Page	1929
Ending Page	1935
Page Count	7
File Format	HTM / HTML PDF
ISSN	14770520
Volume Number	8
Issue Number	8
Journal	Organic & Biomolecular Chemistry
DOI	10.1039/c000965b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	DMSO Marcus theory Imidazole Benzimidazole Dimethyl sulfoxide Acetonitrile 4-Dimethylaminopyridine DABCO Benzotriazole
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Physical and Theoretical Chemistry

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