Sulfanyl-Substituted [3]Cumulenes and Buta-1,3-dienes from a Tetrakis(pyridinium)-Substituted Butadiene

Abstract

Treatment of perchlorobuta-1,3-diene with 4-(N,N-dimethylamino)pyridine resulted in the formation of 1,1¢,1¢¢,1¢¢¢-(2,3-dichlorobuta-1,3-diene-1,1,4,4-tetrayl)tetrakis[4-(dimethylamino)pyridinium] tetrachloride (structure confirmed by X-ray analysis), which was converted into persulfurated butatrienes ([3]cumulenes), pentakis(sulfanyl)-substituted buta-1,3-dienes, or tetrakis(sulfanyl)-substituted 2,3-dichlorobuta-1,3-dienes by reactions with thiolates or a sulfinate. The outcome of the reaction depends on the reaction conditions and the substitution pattern of the starting sulfur nucleophiles.

The Synthesis and Characterization of Some Novel Thioethers: Thio-Subsituted [3]Cumulenes, -1-Buten-3-ynes and Buta-1,3-dienes

“…Oxidation of sulfide compound 4b was carried out using with 1 equivalent of metachloroperbenzoic acid (M-CPBA) to yield the sulfoxide compound 10b at 0 o C. The IR spectrum of 10b showed characteristic absorption of . There are limited reports in the literature on the synthesis of (thio)subsituted [3]cumulene compounds. Herein, we report the synthesis of novel mono-, bis-, tris-and tetrakis-(thio) subsituted [3]cumulene compounds by the reaction of thio(subsituted)-buta-1,3-diene with thiols.…”

“…There are limited reports in the literature on the synthesis of (thio)subsituted [3]cumulene compounds. Herein, we report the synthesis of novel mono-, bis-, tris-and tetrakis-(thio) subsituted [3]cumulene compounds by the reaction of thio(subsituted)-buta-1,3-diene with thiols. As shown Scheme 2, some synthesized [3]cumulene compounds converted into partially butenyne compounds.…”

“…Herein, we report the synthesis of novel mono-, bis-, tris-and tetrakis-(thio) subsituted [3]cumulene compounds by the reaction of thio(subsituted)-buta-1,3-diene with thiols. As shown Scheme 2, some synthesized [3]cumulene compounds converted into partially butenyne compounds. It is known that an allenyl cation is involved as an intermediate in the room-temperature isomerization of butatriene to butenyne.…”

“…3 In addition, it is known that sulfoxides 4 and 1,3-Enynes 5 are useful synthetic intermediates in the synthesis of natural products.…”

“…[6][7][8][9][10][11][12][13][14][15][16] We describe herein the synthesis of mono-, bis-, tris-or tetrakis-(thio)substituted butadienes, butenynes and [3]cumulenes and their bromination, iodination or oxidation.…”