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Nitrogen as Leaving Group: Dediazoniations of Aromatic Diazonium Ions
Ist Teil von
Angewandte Chemie (International ed.), 1978-03, Vol.17 (3), p.141-150
Ort / Verlag
Zug: Hüthig & Wepf Verlag
Erscheinungsjahr
1978
Link zum Volltext
Quelle
Wiley Online Library
Beschreibungen/Notizen
On heating, aromatic diazonium salts eliminate nitrogen by two fundamentally different mechanistic pathways, i.e. heterolysis and homolysis. Among these pathways a series of variants are known, giving rise to a whole variety of mechanisms. This article considers the effect of specific solvation, apparently characteristic of diazonium ions, by various solvents (fluorinated alcohols, methanol, water, dimethyl sulfoxide, pyridine, and hexamethylphosphoric triamide) on the mechanism. Apart from the donor properties of the solvent, the oxidation potential and the presence of additives play a major role in determining what reaction type will predominate.
One of the best nucleofugic leaving groups is N2. Solvent is found to exert a mechanism‐determining effect on thermal elimination of N2 from aromatic diazonium salts: whether the reaction follows a homolytic or a heterolytic course generally depends upon the specific solvation.