1,2-Ditellurolane: A new synthetic method, structure and chemical reactions

Abstract

A simple method for the synthesis of 1,2-ditellurolane is proposed, based on the reaction of elemental tellurium with 1,3-dihalopropane in a system of hydrazine hydrate and alkali followed by the effect of organic solvent on the first formed poly(trimethyleneditellurides). The products of the oxidation and reduction of 1,2-ditellurolane were characterized and its spectral characteristics were analyzed.The reaction of elemental sulfur with alkenylbenzenes, leading to the formation unique heterocyclic compounds -phenyl-substituted 1,2-dithiole-3-thiones -was discovered by M. G. Voronkov in the middle of the last century [1][2][3][4]. Then under his quindance 1,2-dithiol-3-one [5] and 1,2-diselenol-3-one [6] were prepared. This made possible the development of the synthetic chemistry of heterocycles with two chalcogen atoms which possess aromatic properties. Many of these or their derivatives were used in organic synthesis [7] and also as biologically active compounds [8] or industrial products [9].Saturated heterocyclic systems containing two chalcogen atoms (1,2-dichalcogenolans) have been far less studied. This is explained by the difficulty of making and separating them, especially the selenium and tellurium analogs. A multistage synthesis of 1,2-diselenolane has been described using potassium cyanide [10] or metallic lithium [11]. This compound has found use in organic synthesis, for example, in the preparation of stable cross-linked cyclodextrins with selenium bridges with hydrophobic cavities which are able to form inclusion complexes [12], and also calixarenes containing selenium [13]. The preparation of 1,2-ditellurolane 1 was first reported in 1984 [14]. It was obtained by the reaction of 1,3-dibromopropane with polytelluride anions generated by electrochemical reduction of tellurium and was characterized by UV spectroscopy and mass spectrometry. Subsequently 1,2-ditellurolane was obtained by cyanide activation of tellurium followed by reaction with 1,3-dibromopropane [15]. The product was only characterized in solution. The chemical properties of 1,2-ditellurolane was not mentioned in these papers. _______ * Dedicated to Academician of the Russian Academy of Science Mikhail Grigor'evich Voronkov on his 85 th Birthday. __________________________________________________________________________________________

Synthesis and reductive splitting of tellurium-containing oligomers on the basis of 1-bromo-2-methyl-3-chloropropane

“…Similarly, from the oligomer synthesized by the reaction of 1-bromo-3-chloropropane with tellurium, we have earlier obtained the solutions of 1,2-ditellurolane, which was extremely unstable [12] although could be stabilized in the presence of nitrosodurene [13]. As distinct of that, ditellurolane IV unexpectedly turned out to be much more stable: its solutions remained unchanged (according to the UV and NMR spectroscopy) for 3-4 days, and only after that the precipitate appeared, but the solution retained its intense color for several more days.…”