The synthesis of new thiosubstituted butadienes, butenynes and butatrienes

Abstract

By treatment of the pentachlorobutadiene 1 and of the tetrachlorobromobutadiene 9 with thiolates in ethanol, a very fast and extensive replacement of chlorine was observed even at room temperature. The reaction of 1 with three molar equivalents of thiolates lead to butadienes with two, three, four and five organylthio groups. Tris(thio)-substituted butadienes 3a-c tetrakis (thio)-substituted butadiene 4a were treated with potassium tert-butoxide to form tris(thio)substituted butatrienyl halide compounds 12a-c and tetrakis(thio)-substituted butatriene 14a, respectively. The butatrienyl halides 12a-c obtained partly isomerizes to give butenynes 13a-c at room temperature and without catalyst.