A. A. Tatarinova

Synthesis of new secondary phosphine chalcogenides with bulky substituents from aryl(hetaryl)ethenes, red phosphorus, sulfur, and selenium

Phosphine generated along with hydrogen from red phosphorus and aqueous potassium hydroxide selectively reacts with aryl(hetaryl)ethenes (α-methylstyrene, 2-vinylnaphthalene and 5-vinyl-2-methylpyridine) in superbasic system KOH-DMSO(H2O) to give secondary phosphines. The latter are practically quantitatively oxidized by elemental sulfur or selenium (20–25°C, toluene, 0.5 h), to afford the hitherto unknown secondary phosphine chalcogenides with bulky arylalkyl pyridine and naphthyl substituents.

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.

Chlorination of Secondary Phosphine Selenides with the System CCl 4 /NEt 3

Selenophosphoryl chlorides R2P(Se)Cl are highly reactive selenophosphorylating reagents widely used in the synthesis of organoelement compounds [1–5]. They readily react with alkylmagnesium halides [1], al-cohols [2], amines [3] and other compounds [4, 5] to form tertiary phosphine selenides as well as esters, amides, and salts of selenophosphinic acids: ligands for the design of single-source precursors of nanomaterials [6, 7], efficient iniferters [8], prospective extragents of the rare-earth elements [9] and coordination media for synthesis of semiconducting nanomaterials [10].

Reactions of β,β′-dichlorodiethyl ether with elemental chalcogens and dimethyl dichalcogenides in the system hydrazine hydrate-base

Abstractβ,β′-Dichlorodiethyl ether reacted with elemental selenium or tellurium, as well as with binary chalcogen mixtures (S/Se, S/Te, or Se/Te), activated in the system hydrazine hydrate-base to give oligomeric products containing oxygen and polychalcogenide fragments in the chain. Reductive cleavage of these oligomers gave rise to 3-oxapentane-1,5-dichalcogenols and their methyl derivatives. The latter were also synthesized from β,β′-dichlorodiethyl ether and the corresponding dimethyl dichalcogenides in the system hydrazine hydrate-KOH.

Nucleophilic addition of secondary phosphine sulfides to divinyl sulfoxide and divinyl sulfone

Secondary phosphine sulfides readily undergo addition to divinyl sulfoxide and divinyl sulfone in the presence of KOH (THF, 20–22°C, 1 h) with regiospecific formation of bis[2-(diorganylthiophosphoryl)-ethyl] sulfoxides and sulfones. A dramatic increase in the electrophilicity of the double bond in the monoadduct suggests transfer of the electron-acceptor effect of the thiophosphoryl group directly though space, due to its donor-acceptor interaction with the polarized S-O bond. It was demonstrated by the example of divinyl sulfoxide that, when performed with equimolar amounts of reactants and a weaker base (LiOH), the reaction can be stopped at the stage of formation of the monoadduct.

Radical addition of secondary phosphine chalcogenides to allylamine: Atom-economic synthesis of aminopropylphosphine chalcogenides

Secondary phosphine sulfides and phosphine selenides react with allylamine under the conditions of radical initiation (UV or AIBN) to form the anti-Markovnikov adducts in up to 93 % yield.

Redox reaction of red phosphorus with hydrosulfide anions in DMSO

Received April 3, 2008 LETTERS TO THE EDITOR ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 9, pp. 1816–1818.

Functional Methacryloyloxy Acetals: V. Electrophilic Addition of Carboxylic Acids to 2-Vinyloxyethyl Methacrylate

Mono- and dicarboxylic acids (acetic, methacrylic, E-crotonic, and malonic) quantitatively add to 2-vinyloxyethyl methacrylate under mild conditions (1 wt % CF3COOH, 20–60°C, 1–4 h) according to the Markownikoff rule to give the corresponding mono- and bis-adducts with high regio- and chemoselectivity. The products may be regarded as a new family of functionalized methacrylates.