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Two ways for the synthesis of new representatives of non-symmetric organic phosphites with polyfluoroalkyl substituents were developed based on organic dichlorophosphites. The reaction of polyfluoroalkyl dichlorophosphites with allyl alcohol, proceeding at a temperature of –10–22°C (2 h) in the presence of triethylamine, gave diallyl polyfluoroalkyl phosphites in a yield of 75–77%. Under similar conditions (–30–22°C, 2–4 h, Et3N), alkyl (or aryl) dichlorophosphites reacted with polyfluoroalkanols to form alkyl (or aryl) bis(polyfluoroalkyl) phosphites (yield 56–67%). Unlike diallylpolyfluoroalkyl- and alkylbis(polyfluoroalkyl) phosphites, arylbis(polyfluoroalkyl) phosphites are symmetrized under storage conditions (room temperature, inert atmosphere), forming the corresponding triaryl- and tris(polyfluoroalkyl) phosphites.

The catalyst- and solvent-free reaction between bis(fluoroalkyl) phosphonates and aldimines occurs under mild conditions (20–22 °C, 0.25–4 h) to afford a new family of α-amino polyfluoroalkylphosphonates in up to quantitative yields.

Bis(polyfluoroalkyl) chlorophosphites and polyfluoroalkyl dichlorophosphites react easily with secondary amines (from –40 to –22°C, 1–3 h, CH2Cl2) in the presence or absence of triethylamine to form the corresponding bis(polyfluoroalkyl) diorganylamidophosphites or bis(diorganylamido) polyfluoroalkyl phosphites in the yield of up to 74%. Bis(polyfluoroalkyl) diorganylamidophosphites were also synthesized from diorganylamidodichlorophosphites and polyfluoroalkanols (–25 to –22°C, 2 h, Et3N–CH2Cl2) with a yield of 56–60%.

Polyfluoroalkyl dichlorophosphates react easily with propargyl alcohol under mild conditions (22–62°С, 3 h, pyridine-toluene) to form previously unknown bis(2-propynyl) polyfluoroalkyl phosphates with a yield of 36–41%, a triple bond in which is capable of participating in the azide-alkyne cycloaddition reaction.

Bis[2-(4-pyridyl)ethyl]phosphine reacts with acrylonitrile under mild conditions to form bis[2-(4- pyridyl)ethyl](2-cyanoethyl)phosphine which is readily oxidized in air to the corresponding bis[2-(4-pyridyl)- ethyl](2-cyanoethyl)phosphine oxide. The latter compound reacts with 1,4-dihalobutanes according the scheme of polyquaternization with practically quantitative formation of high-molecular cationic compounds (ionenes) bearing phosphine oxide groups and pyridinium cycles in the main chain. The thus obtained ionenes enter the intermolecular interaction with anionic polyelectrolytes (polyacrylic acid, heparin). They were also found to exhibit antibacterial activity.

Polyfluoroalkyl dichlorophosphates easily react with 1,2- or 1,3-alkanediols in a system pyridine–diethyl ether and afford 2-polyfluoroalkoxy-1,3,2-dioxaphospholane oxides or 2-polyfluoroalkoxy-1,3,2-dioxaphosphorinane oxides. In similar conditions the reaction of methyl dichlorophosphate with 1,2- and 1,3-alkanediols proceeds less effectively.

Alkyl methanesulfonates were for the first time introduced in the reaction of direct phosphorylation of electrophiles with elemental phosphorus in strongly basic media to synthesize alkylphosphinic acids in yields of up to 40%.

Polyquaternization reactions of bis[2-(4-pyridyl)ethyl]phenylethylphosphine oxide and tris[2-(4-pyridyl)ethyl]phosphine oxide with 1,4-dibromobutane were implemented for the first time to give linear (water-soluble) and cross-linked (limitedly water swelling), respectively, representatives of new phosphorus- and nitrogen-containing ionenes. The synthesized linear ionenes react with heparin and polyacrylic acid yielding water-insoluble polyelectrolyte complexes.

The catalyst- and solvent-free reaction between pyridines, alkyl propiolates, and bis(fluoroalkyl) phosphonates occurs under mild conditions (20–52 °C, 1–15 h) to stereo- and regioselectively afford bis(polyfluoroalkoxy)phosphoryl-( E )- N -alkoxycarbonylethenyl- 1,2- or 1,4-dihydropyridines in 65–80% yield depending on the structure of the initial pyridine or fluoroalkylphosphonate and the reaction conditions.

The addition of tris(2-pyridyl)phosphine to tertiary cyanopropargylic alсоhols in water (room temperature, no catalyst, 5 h) is accompanied by elimination of pyridine to give cyanoallyldipyridylphosphinates of E-configuration in 60–73% yield, thus indicating the oxygen insertion of the hydroxyl group into the PC bond of the intermediate (Z)-alkenyldipyridylphosphine oxide.

Diphenyl- or bis(2-phenylethyl)phosphine sulfides and -phosphine selenides react with diallylamine under radical initiation (UV or AIBN) to afford the corresponding diadducts and tetrahydropyrrolylmethyl phosphine chalcogenides. The yield and the ratio of the products depend on the structure of the starting secondary phosphine chalcogenides.

The reaction of tri(2-pyridyl)phosphine with electron-deficient alkynes in water proceeds under mild conditions (40–45 °C, without catalyst, 4–5 h) with liberation of pyridine to give (E)-pyridylvinylphosphine oxides in 45–56 % yields, the only exception being the reaction with cyanophenylacetylene, which affords the corresponding vinylphosphine oxide of Z-configuration in 40 % yield. The reaction is likely triggered by the zwitterion, the adduct of tri(2-pyridyl)phosphine to the electrophilic acetylenes, the carbanionic center of which is then neutralized by a proton from water. The intermediate phosphonium hydroxide finally decomposes to the product.

Secondary phosphine sulfides and phosphine selenides react with allylamine under the conditions of radical initiation (UV or AIBN) to form the anti-Markovnikov adducts in up to 93 % yield.

Diverse alkali metal thioselenophosphinates, M[SeSPR2] (M = Li, Na, K, Rb, and Cs; R = alkyl, aryl, aralkyl, and hetaralkyl), have been synthesized in 78–94 % yields by means of a one-pot multicomponent reaction between secondary phosphanes, sulfur, selenium, and alkali metal hydroxides under mild conditions (room temperature, –50 °C, 0.5 h, EtOH). The molecular and electronic structure of the [SeSPPh2]– anion and its coordination behavior towards Li+, Na+, and K+ cations have been investigated at the B3LYP level of theory. The alkylation of the alkali metal thioselenophosphinates with various organic halides proceeds regiosecifically at the selenium center to form Se–organyl thioselenophosphinates, R2P(S)SeR′ (R′ = Me, Et, Bn, allyl, propargyl), in 78–96 % yields. By the action of molecular iodine, the alkali metal thioselenophosphinates instantly (room temperature, ca. 1 s, 1,4-dioxane) undergo selective Se–Se oxidative coupling to afford the corresponding diselenides, R2P(S)SeSe(S)PR2, in 81–92 % yields. The alkali metal thioselenophosphinates are readily converted into the corresponding ammonium derivatives. Square-planar NiII complexes, Ni[SeSPR2]2 (R = Ph, CH2CH2Ph), have been prepared in 68–81 % yield by the treatment of sodium thioselenophosphinates, Na[SeSPR2], with NiBr2 at room temperature (EtOH/CH2Cl2, 10 min).

Treatment of electron-deficient alkynes with phosphine (II) in water is found to result in unusual formation of pyridylvinylphosphine oxides.

Secondary phosphine selenides react with primary or secondary amines at 60–65 °C in dioxane to give phosphinoselenoic amides.

Received April 3, 2008 LETTERS TO THE EDITOR ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 9, pp. 1816–1818. © Pleiades Publishing, Ltd., 2008. Original Russian Text © B.A. Trofimov, S.I. Verkhoturova, V.L. Mikhailenko, T.I. Kazantseva, S.N. Arbuzova, А.А. Tatarinova, L.V. Klyba, N.K. Gusarova, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 9, pp. 1578–1579.

Reaction of addition of phosphine to multiple bonds represents an obvious alternative to the synthesis of organophosphorus compounds by the use of phosphorus halogenides, opening the route to atomsparing design of various phosphines and their derivatives. In spite of its attractiveness up to now this alternative has not been systematically developed although the addition of phosphine to some alkenes and acetylenes is described in a number of publications [1, 2]. So far nothing is known about the addition of phosphine to vinyl sulfoxides. At the same time, this reaction opens a direct one-step route to difficultly accessible phosphines with sulfoxide groups, promising semilabile chelating ligands [3, 4] and intermediates for preparation of, e.g., radioactive diagnosticums [5–7].

Secondary phosphine selenides react with primary or secondary amines at 60–65 °C in dioxane to give phosphinoselenoic amides.

Phosphine, generated from red phosphorus in the system KOH–H 2 O–toluene, reacts with vinyl ethers under radical initiation (AIBN, dioxane, 78–80 °C, atmospheric pressure) to give tris(2-organyloxyethyl)phosphines, which are transformed to the corresponding phosphine chalcogenides (in up to 73% isolated yield) via the reactions with air oxygen, elemental sulfur or selenium.