One-Pot Vinylation of Secondary Phosphine Chalcogenides with Vinyl Sulfoxides

A facile, one-pot vinylation of secondary phosphine chalcogenides with alkyl(or aryl) vinyl sulfoxides has been elaborated. The vinylation comprises the nucleophilic addition of secondary phosphine chalcogenides to the vinyl sulfoxides (～50 mol% KOH, dioxane, 25–40°C, 1 h) followed by the elimination of sulfenic acids from the adducts (additional equivalent of KOH, 60–70°C, 1.5–2.0 h), the yields of target tertiary vinyl phosphine chalcogenides reaching 92%.     

Synthesis of metal complexes with 2-[bis(2-phenylethyl)-thiophophorylhydroxymethyl]-1-organilimidazoles. Crystal structure of ZnCl2 · 2L

The reactions of Zn(II), Cd(II), Cu(II), Co(II), Pd(II) dichlorides with 2-[bis(2-phenylethyl)thiophosphorylhydroxymethyl]-1-organilimidazoles (L¹–L⁴) were studied. The novel complexes were synthesized and characterized by IR and NMR spectroscopies. Depending on the nature of imidazolephosphinesulfide, both monodentate (at the “pyridine” N(1) atom of heterocycle) and the N,S-bidentate binding of the ligand by a metal can be realized in the above metal complexes. The structure of the complex ZnCl₂ · 2L⁴(I) (L⁴ = 2-[bis(2-phenylethyl)thiophosphorylhydroxymethyl]-1-ethylbenzimidazole) was studied by X-ray diffraction. One of the two independent L⁴ molecules performs the solvate function, while another one, together with two Cl atoms, is coordinated through the atoms N(1) and S to the Zn atom at the vertices of a slightly distorted tetrahedron. The molecule of the complex is united with the solvate molecule into [ZnCl₂L₄]L⁴ associates by strong intermolecular hydrogen bonds to give nonplanar four-membered H-cycle OH₂N.     

Reaction of vinyl sulfoxides with sodium sulfide and polysulfides

Sodium sulfide and polysulfides readily (50–55°C, 3 h, aqueous medium) react with alkyl vinyl sulfoxides to afford bis(alkylsulfinylethyl)sulfides and-polysulfides in up to 75% yield. Under comparable conditions the reaction of divinyl sulfoxide with sodium sulfide proceeds by the mechanism of addition-cyclization and results in 1,4-dithiane-1-oxide and 1,4-oxathiane-4-oxide. Microwave activation of the studied reactions allows to increase their rate and efficiency.     

The reaction of red phosphorus with 1‐bromonaphthalene in the KOH–DMSO system: Synthesis of tri(1‐naphthyl)phosphane

Red phosphorus reacts with 1‐bromonaphthalene in the KOH–DMSO system upon heating (47–70°C, 3 h) to give tri(1‐naphthyl)phosphane in 10% yield. Microwave activation (600 W, 6 min) of the reaction affords the above‐mentioned phosphane in 25% yield. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:198–203, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20671     

Oxidative metal‐free cross‐coupling of secondary phosphine chalcogenides and benzenediols: Synthesis of phosphinochalcogenoic O‐diesters

Benzenediols react with 2 equiv of secondary phosphine chalcogenides in the CCl₄–Et₃N system under mild conditions (50–52°C, 1.5–13 h) to give phosphinochalcogenoic O‐diesters in 62–91% isolated yields. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:322–328, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21020     

An Expedient Access to γ‐Ketophosphine Chalcogenides via the Chemo‐ and Regioselective Addition of Secondary Phosphine Chalcogenides to β,γ‐Ethylenic Ketones

γ‐Ketophosphine chalcogenides, precursors for plethora of novel functionalized phosphine chalcogenides and phosphines, are synthesized by chemo‐ and regioselective addition of secondary phosphine chalcogenides to β,γ‐ethylenic ketones under catalyst‐ and solvent‐free conditions (80–100°C, 8–70 h) in excellent yields. The straightforward superbase‐catalyzed synthesis of starting β,γ‐ethylenic ketones from ketones and acetylenes insures the expedient access to the target γ‐ketophosphine chalcogenides.