Syntheses and Reactions of Polycationically Substituted Azido‐ and Diazidobenzenes

Abstract

The increased reactivity of hexakis[4‐(dimethylamino)‐1‐pyridinio]benzene hexakis(trifluoromethanesulfonate) (1) towards nucleophilic substitution of DMAP+ ligands was used for the syntheses of the corresponding pentacationically substituted azidobenzene and the tetracationically substituted o‐diazidobenzene. In contrast to unsubstituted azido‐ and diazidobenzene, the latter compounds are stable towards heat or shock. Predominantly due to the strong electrostatic effects provided by the polycationically substituted phenyl(ene) moieties, the corresponding triphenylphosphazides are stable at room temperature. Application of the Staudinger reaction yielded the corresponding polyonio‐substituted aniline and o‐phenylenediamine, respectively.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Stabilised phosphazides

“…The structure of 14 was unambiguously established by NMR spectroscopy, FAB mass spectrometry and elemental analysis. Phosphazide 14 slowly extrudes dinitrogen in refluxing acetonitrile to give the corresponding phosphazene 15 in 86% yield after 3 days (decomposition starts at 34 • C in the solid state) [19]. Upon reaction with two equivalents of triphenylphosphine under the same conditions, the related orthodiazide 16 does not lead to the ortho-bisphosphazide but to a mixed adduct 17 featuring one phosphazide group and one phosphazene unit.…”