チオアミニル安定ラジカルの合成とその挙動について
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概要
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Syntheses of thioaminyls, a new class of persistent nitrogen-centered free radicals are described. Some aromatic thioaminyls have been isolated as the pure radical crystals or hydrazine-like dimers whose structures have been analysed by X-ray crystallographic method. The Δ<I>H</I>° and Δ<I>S</I>° values for dimers ↔ radicals equilibria have been determined. The relatively low Δ<I>H</I>° values are interpreted in terms of the resonance stabilization by -N-S-↔-N-S<SUP>+</SUP>-conjugation. Aliphatic thioaminyl radicals (RNSR) have also been studied by ESR spectroscopy. When R =R=<I>t</I>-Bu, the corresponding radical was very persistent. Ab initio molecular orbital calculations for a model radical, H-N-S-H, predict that the most stable conformation is a trans planar structure.<BR>To examine the reactivity of thioaminyls reactions of the radicals with phenols, heterocycles, and alkenes have been carried out. The results are briefly described.
- 社団法人 有機合成化学協会の論文