S. I. Shaikhudinova

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.

Regio- and stereospecific addition of phosphines to cyanoacetylenes

Abstract Primary and secondary phosphines add regio- and stereospecifically to phenylcyanoacetylene and 4-hydroxy-4-methylpent-2-ynenitrile under mild conditions to form corresponding functionalized secondary and tertiary phosphines of Z -configuration in 70–91% yield. According to ESR and UV data, the addition of primary phosphines to phenylcyanoacetylene involves a single electron transfer process.

TRIS[(5-CHLORO-2-THIENYL)METHYL] PHOSPHINE OXIDE FROM ELEMENTAL PHOSPHORUS AND 2-CHLORO-5-(CHLOROMETHYL) THIOPHENE

Abstract White phosphorus readily reacts with 2-chloro-5-(chloromethyl)thiophene under phase-transfer conditions (KOH, water, dioxane, benzyltriethylammonium chloride, 50–52°C, 3 h) to form tris[(5-chloro-2-thienyl)methyl]phosphine oxide in good yield. This new phosphine oxide undergoes the Wittig - Homer reaction with benzaldehyde (NaNH2/THF system) leading to 2-chloro-5-|(E)-2-phenylethenyllthiophen and bis[(5-chlom-2-thienyl)methyl]phosphinic acid.

Phosphorylation of Allyl Halides with White Phosphorus

White phosphorus reacts with allyl bromide in the system KOH-dioxane-H 2 O at room temperature to form tris(propen-2-yl), bis(propen-2-yl)(E-propen-1-yl), and bis(E-propen-1-yl)(propen-2-yl)phosphine oxides in a total quantitative yield, their molar ratio being 1:0.5:0.1.

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%.

Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Systems: XV. Phosphorylation of Allyl Halides with Elemental Phosphorus

Elemental phosphorus (red or white) reacts with allyl chloride and allyl bromide in a two-phase system aqueous KOH-organic solvent to form tertiary symmetrical and mixed phosphine oxides among which tris(prop-2-enyl)-, bis(prop-2-enyl)[(E)-prop-1-enyl]-, bis(prop-2-enyl)[(Z)-prop-1-enyl]-, (prop-2-enyl)[(E)-prop-1-enyl][(Z)-prop-1-enyl]-, bis[(E)-prop-1-enyl](prop-2-enyl)-, bis[(Z)-prop-1-enyl](prop-2-enyl)-, tris-[(E)-prop-1-enyl]-, and bis[(E)-prop-1-enyl][(Z)-prop-1-enyl]phosphine oxides were identified. The conditions (room temperature, 60% aqueous KOH-dioxane) allowing preparation from white phosphorus and allyl bromide of tris(prop-2-enyl)- and bis(prop-2-enyl)[(E)-prop-1-enyl]phosphine oxides as major products in the total yield of up to 96% were found.

Biographical radiation-induced defect formation as a method for the activation of red phosphorus in reactions with arylalkenes

In recent years, it has been reported that the modifica tion of the chemical properties of red phosphorus (both in inorganic1—2 and organic3—6 processes) can be regulated by controlled defect formation in its structure. New data on the effect of biographical defects on the reactivity of elementary phosphorus were obtained in di rect phosphorylation of arylalkenes in a KOH—DMSO system. Red phosphorus *Pn synthesized by radiation induced polymerization of white phosphorus in benzene (with 60Co as the radiation source) and containing P— P—R type defects (R is a benzene fragment)5 reacts with styrene at room temperature to give diphenethylphosphine oxide (1) and phenethylphosphinic acid (2) in a total yield of 15%. With commercial red phosphorus Pn pro duced by thermal polymerization of white phosphorus, the total yield of organophosphorus compounds 1 and 2 did not exceed 2%. Under similar conditions, white phos phorus P4 is more reactive: the total yield of compounds 1 and 2 is 30%. In phosphorylation of 2 vinylnaphthalene (90—96 °C), defective *Pn is superior to both Pn and P4 to give tris[2 (2 naphthyl)ethyl]phosphine oxide (3), 2 (2 naph thyl)ethylphosphinic acid (4), and bis[2 (2 naph thyl)ethyl]phosphine oxide (5) as the major reaction prod ucts in a total yield of 73% (product ratio 1.6 : 1.2 : 1). Under comparable conditions, phosphorylation of 2 vinylnaphthalene with P4 or Pn is less efficient but more selective (phosphine oxide 3 is formed in 58 and 44% yield, respectively). In addition, the above reaction with Pn affords acid 4 in 11% yield. The formation of oxygen containing compounds 1—5 seems to be in accord with the proposed mechanism.7 Compounds 1—5 were isolated and identified by com paring their 1H and 31P NMR spectra (Bruker DPX 400; 400 and 161.98 MHz, respectively; CDCl3) with spectro scopic data for authentic samples.8,9

Reactivity of primary and secondary alcohols in nucleophilic addition to a triple bond: the vinylation of butane-1,3-diol

Acetylene adds to butane-1,3-diol in the presence of KOH to give, along with the corresponding divinyl ether and 2,4-dimethyl-1,3-dioxane, 4-vinyloxybutan-2-ol and its structural isomer 3-vinyloxybutan-1-ol, the ratio between the latter two products, (5–8)∶1, depending on the reaction conditions.

Synthesis and antibacterial activity of tris{2-[4-(1-benzylpyridinio)]ethyl}-phosphinoxide trichloride

Recently we have demonstrated that triorganyiphosphine oxides containing pyridinium fragment possessed pronounced antibacterial activity [1]. This work was devoted to the search for new efficient antibacterial agents in this series of organophosphorus compounds. For this purpose we have developed a method for the synthesis of tris{2-[4-(l-benzylpyridinio)]ethyl}phosphinoxide trichloride (1I) (previously unreported) and studied its antibacteriai activity. The initial organophosphorus compounds was represented by tris[2-(4-pyridyl)ethyl]phosphinoxide (I), which is readily obtained from red phosphorus and 4vinylpyridine in the presence of a strong base [2]. Heating phosphinoxide 1 with benzylchloride quantitatively yields trichloride I1.

A NOVEL METHOD FOR SYNTHESIZING DIORGANYLPHOSPHINOUS ACIDS FROM RED PHOSPHORUS AND ARYLALKENES

The reaction of styrene and α-methylstyrene with P in aprotic polar solvents in the presence of KOH affords diorganylphosphinous acids.