N. K. Gusarova

NUCLEOPHILIC ADDITION OF PHOSPHINE TO ARYL- AND HETARYLETHENES : A CONVENIENT SYNTHESIS OF BIS(2-ARYLALKYL)- AND BIS(2-HETARALKYL)PHOSPHINES

Abstract A number of secondary phosphines [RCH(R′)CH 2 ] 2 PH (R = aryl or hetaryl, R′ = H or Me) have been obtained in good yields by introducing phosphine at normal pressure into a mixture of the alkenes R(R′)CCH 2 , potassium hydroxide and dimethylsulfoxide.

Novel general halogen-free methodology for the synthesis of organophosphorus compounds

The use of novel general halogen-free methodology for the synthesis of phosphines, phosphine chalcogenides, and phosphinic acids from elemental phosphorus and alkenes and alkynes in the superbase suspensions is described.

Alkylvinyl tellurides from tellurium, acetylene and alkyl halides

Abstract Synthetic routes to alkylvinyl tellurides by direct reaction of metallic tellurium, acetylene and alkyl halide in the system KOH-SnCl2-H2O and successive interaction of divinyl telluride with lithium and alkyl halide in liquid ammonia have been developed.

Conformational analysis and stereochemical dependences of 31P–1H spin–spin coupling constants of bis(2-phenethyl)vinylphosphine and related phosphine chalcogenides

Theoretical energy‐based conformational analysis of bis(2‐phenethyl)vinylphosphine and related phosphine oxide, sulfide and selenide synthesized from available secondary phosphine chalcogenides and vinyl sulfoxides is performed at the MP2/6‐311G** level to study stereochemical behavior of their 31P–1H spin–spin coupling constants measured experimentally and calculated at different levels of theory. All four title compounds are shown to exist in the equilibrium mixture of two conformers: major planar s‐cis and minor orthogonal ones, while 31P–1 H spin–spin coupling constants under study are found to demonstrate marked stereochemical dependences with respect to the geometry of the coupling pathways, and to the internal rotation of the vinyl group around the P(X)‐C bonds (X = LP, O, S and Se), opening a new guide in the conformational studies of unsaturated phosphines and phosphine chalcogenides. Copyright

SUPERBASE-INDUCED GENERATION OF PHOSPHIDE AND PHOSPHINITE IONS AS APPLIED IN ORGANIC SYNTHESIS

Abstract A series of new direct reactions of red phosphorus (or white) with organyl halides, alkenes and acetylenes have been developed. Reactions occur in superbasic systems, such as alkali metal hydroxide-dipolar aprotic complexing solvent (DMSO, HMPA) or under phase-transfer conditions to afford earlier inaccessible triorganylphosphines and -phosphine oxides including unsaturated ones in good yields.

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.

Vibrations of the S–S bond in elemental sulfur and organic polysulfides: a structural guide

This review summarizes and analyzes in comparative manner the S–S bond vibrations in IR and Raman spectra of elemental sulfur and organosulfur compounds containing disulfide and polysulfide moieties. It is intentionally biased toward application of the experimental S–S bond frequencies for structural elucidation of sulfur compounds. It was shown that the S–S bond frequencies are a useful tool for identification of the elemental sulfur modifications, organic disufides and polysulfides. Particular attention is paid to the correlation between the S–S bond frequencies and the molecular structure.

Diselenophosphinates. Synthesis and Applications

The last few years have seen a considerable expansion in research on the chemistry of diselenophosphinates (salts and esters of diselenophosphinic acids) due to the use of these compounds as effici...

Synthesis of organic phosphines and phosphine oxides from elemental phosphorus and phosphine in the presence of strong bases

Data on the reactions of elemental phosphorus and phosphine with electrophilic reagents are described systematically and analyzed. These reactions occur in the presence of strong bases and yield primary, secondary, and tertiary phosphines and phosphine oxides.

Addition of secondary phosphines to N-vinylpyrroles

Abstract Secondary phosphines 1 – 3 react readily with N -vinylpyrroles 4 and 5 under radical initiation to give regiospecifically anti-Markovnikov adducts, diorganyl-2-(1-pyrrolyl)ethylphosphines 6a – d , highly reactive building blocks for organic synthesis, in 88–91% yields.