Yu. V. Smetannikov

Effect of the Polarity of the Medium on the Ionic Radiation-Induced Polymerization of Elemental (White) Phosphorus

In recent years, inorganic polymers (red phosphorus, polymeric sulfur and arsenic, compositions based on them, etc.) have been the objects of intensive theoretical and applied studies [1, 2] because elucidation of fundamental characteristics would help to identify the optimal ways of synthesis of these polymers and would contribute to the solution of the general problem of the molecular structure‐inorganic material structure‐material physicochemical properties relationship. Within the framework of the research topic of radiation-induced chemical synthesis of inorganic phosphorus polymers and materials with specified properties based on them, we studied the radiation-induced polymerization of white phosphorus in nonpolar media (benzene, halohydrocarbons, and hexane) [3]. The process was shown to follow a radical mechanism.

Reactions of Elemental Phosphorus and Phosphines with Electrophiles in Superbasic Systems: XIII. Phosphorylation of Phenylacetylene with Active Modifications of Elemental Phosphorus

Phosphorylation of phenylacetylene with white or activated red phosphorus (prepared from white phosphorus under the action of ionizing radiation) occurs in KOH-DMSO or KOH-HMPA systems with heat evolution and stereoselective formation of Z isomers of tristyrylphosphine and -phosphine oxide in yields of 48-49% and 10-15%, respectively. Under the comparable conditions the commercial red phosphorus is considerably less reactive toward phenylacetylene: The total yield of the above-mentioned products is 5%.

REACTION OF VINYLPYRIDINES WITH ACTIVE MODIFICATIONS OF ELEMENTAL PHOSPHORUS IN KOH/DMSO

The phosphorylation of 2-vinyl- and 4-vinylpyridines by white phosphorus and active modifications of red phosphorus (obtained by thermal polymerization of white phosphorus in the presence of graphite or the action of ionizing radiation in benzene) in the KOH/DMSO superbase system at room temperature leads to the formation of tris[2-(2-pyridyl)ethyl]- and tris[2-(4-pyridyl)ethyl]phosphine oxides in 58-72% yield. These oxides are promising ligands for design of metal complex catalysts. These vinylpyridines react less efficiently with ordinary red phosphorus and the yield of the corresponding tris(2-pyridylethyl)phosphine oxides does not exceed 10%.

Reaction of Activated Red Phosphorus with Allyl Bromide under Phase-Transfer Catalysis

Common red phosphorus (Pn) reacts with allyl halides (bromide and chloride) on heating (45 75 C) under phase-transfer catalysis to form mixtures of tertiary unsaturated phosphine oxides (total yield up to 23%), among which products of prototrophic isomerizations of tri(propen-2-yl)phosphine oxide (I) prevail. These are di(propen-2-yl)[(E)-propen-1-yl]-, di(propen-2-yl)[(Z)-propen-1-yl]-, (propen-2-yl)[(E)propen-1-yl][(Z)-propen-1-yl]-, di[(E)-propen-1-yl](propen-2-yl)-, di[(Z)-propen-1-yl](propen-2-yl)-, tri[(E)-propen-1-yl]-, and di[(E)-propen-1-yl][(Z)-propen1-yl]phosphine oxides [1]. At room temperature this reaction gives mainly the kinetically controlled product, phosphine oxide I, in a yield less than 2% (in this case, the phosphorus conversion is 18%) [1].

Radiation chemical synthesis of modified phosphorus-containing polymers

Currently, considerable effort is directed to the search for new environmentally friendly processes needed for successful and sustainable development of industrial chemistry. The organophosphorus chemis� try tends to switch from the use of elemental (white) phosphorus as the phosphorylating agent to less toxic polymeric phosphorus forms with controllable prop� erties. The radiation chemical synthesis of phosphorus� containing polymers (PCP) from white phosphorus in the presence of modifying additives (TiO2, Al(OH)3, CaCl2, talcum Mg3(OH)2[Si4O10], graphite, I2, indus� trial red phosphorus (IRP) etc.) developed in our pre� vious works [1–3] made it possible to solve a number of problems related, in particular, to stabilization of

Reaction of Activated Red Phosphorus with Phenylacetylene in the KOH-HMPA System

Crude (commercial) red phosphorus reacts with phenylacetylene upon heating (60365oC) in a system the KOH3HMPA3H2O to yield 50% of tris[(Z)-styryl)phosphine and small amounts of the corresponding tris[(Z)-styryl)phosphine oxide [1]. Phosphorylation of phenylacetylene with phosphine generated separately from crude red phosphorus and KOH in water3dioxane medium proceeds under milder conditions (553 57oC), yielding 70% of phosphine I [2].