Chemistry of polyhalogenated nitrobutadienes, 4: reactions of mono-, bis-, and tris(4-tolylthio) derivatives of 2 nitroperchloro-1,3-butadiene with α,β-bifunctional nucleophiles

Abstract

The reaction of 1-(4-tolylthio)-, 1,1-bis(4-tolylthio)-, or 1,1,3-tris(4-tolylthio)perchloro-2-nitro-1,3-butadiene with ,-bifunctionalized ethanes such as N,N-, N,O,-, N,S-, O,S-, S,S-, or O,Obisnucleophiles leads to both, highly functionalized 2-(1-nitroallylidene) derivatives of imidazolidine, oxazolidine, thiazolidine, [1,3]oxathiolane, or [1,3]dithiolane, respectively, and to the open chain, next higher thiolated buta-1,3-diene. The product distribution is highly sensitive to modifications of the reaction conditions: apart from changes of molar ratios of substrates and reagents the reaction temperature plays an important role. Thus, increase of the reaction temperature favours formation of the 1,3-heterocyclic ring. In all cases, extensive spectroscopic investigations have been performed and, in the case of the [1,3]oxathiolane also an X-ray analysis.