General Papers ARKIVOC 2007 (i) 76-93 ISSN 1424-6376 Page 76 © ARKAT USA, Inc. 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 Viktor A. Zapol’skii, a Jan C. Namyslo, a Mimoza Gjikaj, b and Dieter E. Kaufmann a* a Institute of Organic Chemistry, Clausthal University of Technology, D-38678 Clausthal-Zellerfeld, Germany b Institute of Inorganic and Analytical Chemistry, Clausthal University of Technology, D-38678 Clausthal-Zellerfeld, Germany E-mail: dieter.kaufmann@tu-clausthal.de 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 α,β-bifunctionalized ethanes such as N,N-, N,O,-, N,S-, O,S-, S,S-, or O,O- bisnucleophiles 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. Keywords: 2-Nitro-perchloro-1,3-butadiene, imidazolidine, thiol, vinylic substitution, nmr spectroscopy, X-ray structure Introduction Due to their stepped reactivity in S N reactions, nitro-substituted polyhalogeno-1,3-butadienes have proven to be valuable synthetic precursors for a variety of polyfunctionalized bioactive heterocycles. 1,2 Often times, the building block of choice is 2-nitroperchloro-1,3-butadiene (1) which is easily accessible by the introduction of an activating and directing nitro group into 2H- pentachloro-1,3-butadiene. Synthetic use of 1 opens access to a quite diverse chemistry, the documentation of which has been started by our group recently. 1 The preferred primary reaction center of 1 is the activated terminal carbon atom C-1 of the nitrodichlorovinyl moiety. This