Reaction of Mono- and Dihaloalkanes with Mixed Solutions of Chalcogens in Alkaline Reductive Systems

Sufur-selenium, sulfur-tellurium, selenium-tellurium, and sulfur-selenium-tellurium mixtures readily dissolve in the hydrazine hydrate-alkali system to form chalcogenide anions. Alkylation of the latter with ethyl bromide results in preferential formation of diethyl disulfide, diethyl diselenide, and diethyl ditelluride. Tellurium reacts with dichloromethane in the presence of sulfur, yielding poly(methylene ditelluride), the reaction in the presence of selenium gives rise to poly(methylene selenotellurides), while in the sulfurselenium-tellurium mixture polymers containing all the components are formed.     

Thiylation of Functionalized Electrophiles with Sulfur in Basic Reductive Systems

Functionalized electrophiles, specifically acetyl chloride, benzoyl chloride, chloroacetylchloride, benzenesulfonyl chloride, and N,N,4-trichlorobenzenesulfonamide, were brought into reaction with sulfur in the systems hydrazine hydrate-NaOH and sodium sulfide-water-ethanol. The efficiencies of these systems were compared. The reaction of chloroacetyl chloride with sulfur in the system hydrazine hydrate-base afforded new types of polymeric compounds, poly[(diacylhydrazine)polysulfides]. The reaction mechanisms were discussed.     

New Routes to Poly(Alkylene Sulfidoselenides)

A procedure was developed for preparing mixed poly(alkylene sulfidoselenides) by simultaneous dissolution of sulfur and selenium in basic reducing systems NaOH (KOH)-N₂H₄·H₂O-H₂O, followed by alkylation of the resulting solutions with bielectrophilic agents.     

A mechanism of the hydrogenation of the double bond in the synthesis of allyl chalcogenides in the hydrazine hydrate-potassium hydroxide system

Allyl halides react with elemental selenium in the N₂H₄·H₂O−KOH system to give diallyl chalcogenides and allyl propyl chalcogenides. The latter form only in the presence of oxygen when unsaturated intermediates CH₂=CHCH₂YK (Y=S and Se), which are soluble in hydrazine hydrate, are hydrogenated with diimide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1874–1876, September, 1998.     

Reaction of Diethyl Diselenide with Dihaloalkanes in an Alkaline Reductive Medium

Bis(ethylseleno)alkanes were obtained by reductive cleavage of the Se-Se bond in diethyl diselenide with the system hydrazine hydrate-alkali, followed by alkylation with dihaloalkanes. A general preparative method of synthesis of bis(alkylseleno)alkanes of various structure was proposed.     

Reaction of Aldehydes with Hydrazine in the System Sulfur-Alkali

Dissolution of sulfur in the system hydrazine hydrate-alkali leads to strong activation of hydrazine, so that the latter readily reacts at room temperature with aldehydes of the aromatic and thiophene series to give the corresponding aldehyde azines in high yield. The mechanism of activating effect of sulfur is discussed.