A. V. Artem’ev

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.

Asymmetric configurations of a thin current sheet with a constant normal magnetic field component

A possible mechanism for the formation of a quasi-equilibrium asymmetric current sheet in the magnetospheric tail due to the asymmetry of peripheral plasma sources is analyzed using a self-consistent particle- in-cell model of a thin collisionless current sheet with a constant normal magnetic field component. For the case in which the current sheet is produced by only one source, quasi-equilibrium sheet configurations with maximum possible asymmetry are obtained for different input parameters of the model. In such configurations, the equilibrium force balance is satisfied with high accuracy and the shape of the current density profile remains nearly symmetric, but the current sheet itself is slightly shifted from the source as compared to the symmetric case. The configurations obtained using numerical simulations are compared with those calculated using the previous analytical model of a thin current sheet. It is found that the results provided by these models agree well both qualitatively and quantitatively.

First example of the \( C_{sp^2 } \)-P bond formation in the reaction of red phosphorus with hetaryl halides

Direct reactions of red and white phosphorus with electrophiles (aryland hetarylalkenes, arylacetylenes, alkyl, allyl, and benzyl halides) in superbasic systems alkali metal hydroxide – dipolar aprotic solvent (DMSO, HMPTA) or under the conditions of phase transfer catalysis are now considered as a novel chlorine-free method of formation of the С–P bond [1, 2]. Within this approach, the one-pot methods have been elaborated for the synthesis of various phosphines, phosphine oxides, and phospinic acids [1, 2] which had earlier been obtained by multistep processes from phosphorus halides. However, in the case of the substitution reaction only the Сsp3–P bond was formed. Recently, tris(1-naphthyl)phosphine was synthesized from red phosphorus and 1-naphthyl bromide in the system KОН–DMSO [3]. To the best of our knowledge, there are no data in the literature on the formation of the Сsp2–P in the reactions of elemental phosphorus with hetaryl halides in superbasic systems.

Nucleophilic addition of phosphine to 4-chlorostyrenes in the KOH-DMSO system

In the superbasic system KOH-DMSO (H2O) at 60–75 °C (2–2.5 h, atmospheric pressure), 4-chlorostyrene and 4-chloro-α-methylstyrene add phosphine at the double bond to form 1: 1 and 2: 1 anti-Markovnikov adducts in 10–18% and 58–67% yields, respectively.

Synthesis of [2-(methoxyaryl)-1-methylethyl]phosphinic acids from red phosphorus and (allyl)(methoxy)benzenes

Abstract(Allyl)(methoxy)benzenes react with red phosphorus in the superbasic system KOH-DMSO in the presence of small amounts of water and hydroquinone (3 h, 130 °C) to regio- and chemoselectively give [2-(methoxyaryl)-1-methylethyl]phosphinic acids in preparative yields up to 52%. The reactions involve isomerization of allylbenzenes into (prop-1-enyl)benzenes.

Synthesis of tris(2-pyridyl)phosphine from red phosphorus and 2-bromopyridine in the CsF-NaOH-DMSO superbasic system

164 Pyridylphosphines are widely used as polydentate chemolabile P,N ligands for the design of multipur pose metal complex catalysts [1–3], highly reactive building blocks in organic synthesis [4], and precur sors in the preparation of new pharmaceuticals [5, 6]. Among pyridylphosphines, tris(2 pyridyl)phosphine is of special interest as a tripodal ligand of chelating type due to the geminal arrangement of the nitrogen atoms with respect to the phosphorus atom. Metal complexes obtained from tris(2 pyridyl)phosphine are efficient catalysts for industrially important processes, such as alkene hydroformylation [7], ethylene poly merization [8], methoxycarbonylation of acetylenes [9], and diene synthesis [10].

Novel quinine, lupinine, and anabasine derivatives containing dithiophosphinate groups

A three-component, atom-economic reaction between natural quinine, lupinine, or anabasine, secondary phosphines, and elemental sulfur occurs under mild conditions to yield previously unknown optically active dithiophosphinates.

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].

Novel method for the synthesis of diselenophosphinates

225 Alkali metal and organylammonium diseleno phosphinates are convenient precursors for semi conducting [1] and magneto optical [2] nanomate rials, ligands for designing metal complexes [3], promising extractants of rare and transuranium ele ments [4], potential biologically active compounds [5], and building blocks for organic synthesis [6]. At the same time, the known methods for their prepa ration are multistep and laborious and based on the use of toxic, corrosive, and not readily available compounds [1, 7–9]. For example, sodium diphe nyldiselenophosphinate was obtained as a solvate [Na(Se2PPh2) · THF · 5H2O] in low yield from chlorodiphenylphosphine, sodium metal, and ele mental selenium in liquid ammonia [9]. Similar potassium salt results as a monohydrate [К(Se2PPh2) · H2O] from the reaction of potassium diphenylphosphide (obtained by the cleavage of Ph3P with potassium metal K) with elemental sele nium [2]. Triethylammonium diphenyldiseleno phosphinate [Ph2PSe2][HNEt3] was isolated from a complex reaction mixture resulting from the treat ment of chlorodiphenylphosphine with a triethylsi lane–triethylamine system (ambient temperature, 6 h) followed by refluxing the reaction products with elemental selenium (toluene, 20 h) [1].

Nanobiocomposite based on selenium and arabinogalactan: Synthesis, structure, and application

Nanocomposite of heteropolysaccharide arabinogalactan and elemental selenium (0.54% of Se) has been prepared and studied by means of transmission electron microscopy, UV spectroscopy, and X-ray diffraction analysis. Possibility of the composite application for treatment of bone injury has been estimated.