Unusual Thermolysis of Diisobutyl Polysulfides

Russian Journal of Organic Chemistry -     

2,5-dihalothiophenes in the reaction with chlorosulfonic acid

The mixtures of mono-and dihalothiophenesulfonyl chlorides, formed in the sulfochlorination reaction of 2,5-dichlorothiophene and 2,5-dibromothiophene, were treated with aqueous ammonia and thus converted into mixtures of the corresponding stable thiophenesulfonamides. The structure and composition of the latter were studied by physicochemical methods: GC-MS and ¹H, ¹³C, ¹H-¹³C HSQC, ¹H-¹³C HMBC, and NOESY NMR spectroscopy. As a result of the above chemical transformations, 2,5-dichlorothiophene afforded a mixture of 5-chlorothiophene-2-sulfonamide and 4,5-dichlorothiophene-3-sulfonamide in a roughly 70:30 ratio. In the case of 2,5-dibromothiophene, a mixture of 5-bromothiophene-2-sulfonamide, 4,5-dibromothiophene-3-sulfonamide, and 3,5-dibromothiophene-2-sulfonamide (3:54:43) was formed. Original Russian Text I.B. Rozentsveig, Yu.A. Aizina, K.A. Chernyshev, L.V. Klyba, E.R. Zhanchipova, E.N. Sukhomazova, L.B. Krivdin, G.G. Levkovskaya, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 5, pp. 831–836.     

Synthesis and redox activity of sulfurized poly(methylene polysulfides)

Redox-active sulfurized poly(methylene polysulfides) ?[CH₂S _y ] _n ? (y = 4–22) were prepared by deep sulfurization of poly(methylene di- and trisulfides) with elemental sulfur. The use of the substances obtained as an active cathode material of rechargeable lithium cells ensures their cycling with a specific discharge capacity of 418–550 mA h g^?1.     

High-Temperature Synthesis of Thiophene from Bis(2-chloroethyl) Sulfide

Gas-phase reaction of bis(2-chloroethyl) sulfide (Yperite) with acetylene at 550–700°C leads to formation of thiophene in 45% yield, the conversion of the initial sulfide being complete. The yield of thiophene reaches 63–68% in the thermolysis of a mixture of acetylene, bis(2-chloroethyl) sulfide, and lower organic disulfides.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 910–912.Original Russian Text Copyright © 2005 by Voronkov, Levanova, Sukhomazova, Russavskaya, Deryagina, Korchevin.     

Gas-phase Reaction of 2-Chlorothiophene with Hydrogen Sulfide in the Presence of Alcohols

The effect of methanol and ethanol on the route of the gas-phase reaction of 2-chlorothiophene with hydrogen sulfide, leading to 2-thiophenethiol and to bis(2-thienyl) sulfide, has been investigated. It was found that methanol significantly enhances this reaction and increases its selectivity for the thiol at higher temperatures than without the initiator. The optimal conditions were achieved at 570°C in the presence of 10 mole % of methanol when the conversion of the 2-chlorothiophene in the reaction with hydrogen sulfide reaches 98% and the yield of the thiophenethiol (43%) exceeds that of the bis(2-thienyl)sulfide (31%). In the absence of methanol the 2-thiophenethiol is formed only at 510-540°C in just 17% yield, the basic reaction product being the indicated sulfide (52% yield); the conversion of the 2-chlorothiophene does not exceed 54%.     

Thermal reactions of organyl chalcogenides with α,β-unsaturated aldehydes

Thermal gas-phase reactions of acrolein, cinnamaldehyde, and benzaldehyde with diorganyl chalcogenides and diorganyl dichalcogenides were studied. Acrolein does not react with chalcogenides at 300–600°C but completely decomposes under reaction conditions. At 600–650°C, cinnamaldehyde reacts only with diorganyl selenides and diselenides to give benzoselenophene. Its highest yield (53%) is achieved in the reaction with dimethyl diselenide at 630°C and at an equimolar ratio of the reactant. The gas-phase reactions of benzaldehyde at 400–500°C afford chalcogen-containing derivatives of several types, among which thioanisole and its selenium or tellurium analogs predominate. The mechanisms of the above reactions were discussed in terms of homolytic substitution of the formyl group at unsaturated carbon atoms by chalcogenyl radicals.     

Stabilization of 1,2-ditellurolane by 2,3,5,6-tetramethylnitrosobenzene (Nitrosodurene)

1,2-Ditellurolane is an extremely unstable heterocyclic compound which can be maintained in solution in the presence of nitrosodurene for several days. It is proposed on the basis of UV spectroscopy and ¹H NMR spectroscopy that a complex is formed which determines the stability of 1,2-ditellurolane. It is shown that stabilized 1,2-ditellurolane can be used in organic synthesis. Presented to Academician of the Russian Academy of Sciences Boris Aleksandrovich Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, 1736–1738, November, 2008.     

Synthesis and oxidative cleavage of poly(trimethylene diselenides)

1-Bromo-3-chloropropane and elemental selenium react in hydrazine hydrate-alkali and hydrazine hydrate-amine systems to form poly(trimethylene diselenides). The reductive cleavage of the resulting selenokols yielded 1,3-propanediselenol, 1,2-diselenolane, and bis(alkylseleno)propanes. These compounds are important reagents for organic synthesis and ligands for complex formation. The products obtained were studided by GC-MS.     

Chloromethylation of Bis(2-thienyl) Sulfide

Chloromethylation of bis(2-thienyl) sulfide is accompanied by fast polycondensation of the primary chloromethylation product with the initial sulfide. The reaction gives a new polymer in which the thiophene rings are alternately separated by sulfur atoms and methylene groups. Fusion of the polymer with molecular sulfur gave new sulfur-enriched polymers whose specific electric conductivity is comparable with that of organic semiconductors.