N. V. Russavskaya

Synthesis and oxidative cleavage of poly(trimethylene diselenides)

Abstract1-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.

Reactions of 2,3-dichloro-1-propene with sulfur and tellurium in the system hydrazine hydrate-KOH

Abstract2,3-Dichloro-1-propene reacts with sulfur dissolved in the system hydrazine hydrate-KOH (with formation of K2S2 or K2S) to afford bis(2-chloro-1-propene-3-yl)sulfide as the main product in both cases. Under similar conditions tellurium induces β-elimination of both chlorine atoms resulting in the formation of allene and complete regeneration of tellurium metal.

Reaction of 1-bromo-3-chloropropane with tellur and dimethyltelluride in the system of hydrazine hydrate-alkali

A synthesis of oligomeric substance of thiocol type, the poly(trimethyleneditelluride), from 1-bromo-3-chloropropane and elemental tellurium is performed using a hydrazine hydrate-alkali system. Reductive splitting of the tellurocol followed by alkylation with methyl iodide give rise to preparation of bis(methyltelluro)propane, which was synthesized also from dimethyltelluride and 1,3-dihalopropanes using the N2H4·H2O/KOH system. Mass spectra of the synthesized low molecular weight organotellurium compounds are considered.

Features of the reaction of 2,3-dichloroprop-1-ene with selenium in a hydrazine hydrate-base systems

The direction of the reaction of sulfur with 2,3dichloro-1-propene I in the hydrazine hydrate–base system was shown to depend on the nature of the used bases. In the hydrazine hydrate–KOH system (molar ratio KOH:S = 1:1) the reaction with dichloride I affords bis(2-chloro-1-propen-3-yl)sulfide (78%) [1]. The disulfide anion generated in the system hydrazine hydrate–monoethanolamine reacts with dichloride I to give bis(2-chloro-1-propen-3-yl)disulfide (70%) [2]. Tellurium, which is reduced to the anions Теn only in the hydrazine hydrate–alkali system, reacts with 2,3dichloro-1-propene I with elimination of both chlorine atoms, and the reaction product is allene [1].

Reactions of 1,2-dihaloethanes with chalcogenide anions

Reactions of 1,2-dihaloethanes with chalcogenide anions generated from elemental chalcogens and dimethylchalcogens were performed in the hydrazine hydrate-KOH system. The use of anions Sex2− and Tex2− (x = 1−4) resulted in ethylene evolution and chalcogen regeneration (or in increased x value in an anion). Oligomers of Thiokol type formed only in the reaction of the 1,2-dichloroethane with a mixture of potassium disulfide and diselenide. The reductive cleavage of oligomers obtained in the hydrazine hydrate-KOH system followed by methylation led to the formation of 1,2-bis(methylthio)ethane, 1-methylseleno-2-methylthioethane, and 1,2-bis(methylseleno)ethane. The features of substitution with chalcogenide anions in vicinal dihalides are discussed. Mass spectra of compounds obtained were measured and analyzed.

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.

Synthesis of unsaturated organoselenium compounds via the reaction of organic diselenides with 2,3-dichloro-1-propene in the hydrazine hydrate-KOH system

Dimethyldiselenide reacts with 2,3-dichloro-1-propene at 20–25°C in the hydrazine hydrate-KOH medium to form 2-chloro-3-methylselanyl-1-propene with 90% yield. Diphenyldiselenide in the reaction with 2,3-dichloro-1-propene, depending on the conditions, can give quite selectively four products: 2-chloro-3-phenylselanyl-1-propene, phenylselanylpropadiene, 1-phenylselanyl-1-propyne, and Z-1,2-bis(phenylselanyl)-1-propene. The effect of the selenium atom on the reaction direction and the products structure is discussed.

Domino reaction of 2,3-dichloroprop-1-ene with diphenyl disulfide in the system hydrazine hydrate-potassium hydroxide

Abstract2,3-Dichloroprop-1-ene reacted with diphenyl disulfide in the system hydrazine hydrate-potassium hydroxide at 30–35°C to give three products: 2-chloro-3-phenylsulfanylprop-1-ene, 1-phenylsulfanylpropadiene, and 1-phenylsulfanylprop-1-yne. Variation of temperature ensures selective synthesis of one of the above products, which confirms their successive formation (domino reaction). The domino reaction at 60°C goes further to afford (Z)-1,2-bis(phenylsulfanyl)prop-1-ene.

Chalcogen-containing analogs of ethylene glycol and its derivatives

Ethylene chlorohydrin when reacted with elemental chalcogens or dimethyl dichalcogenides in the hydrazine hydrate-alkali system forms chalcogen-containing analogs of ethylene glycol and its derivatives (dichalcogenated β-diglycols, chalcogenated ethanols, and chalcogenated methyl cellosolves).

New Preparative Procedure for the Synthesis of Chloroalkyl Sulfides

Reaction of thiols with dihaloalkanes in the system hydrazine hydrate-base leads to alkyl(chloroalkyl) sulfides with different positions of the chlorine atom with respect to sulfur. The developed one-step procedure for the synthesis of such unsymmetrical sulfides is most suitable for arenethiols and alkanethiols having a long polymethylene chain. The reaction mechanism is discussed.