Catalytic phosphorylation of polyfluoroalkanols

Catalytic phosphorylation of -polyfluoroalkylbenzyl alcohols with excess 1,1-dihydropolyfluoroalkyl dichlorophosphates afforded (1,1-dihydropolyfluoroalkyl) (-polyfluoroalkylbenzyl) chlorophosphates in a high yield. According to NMR (¹H,¹⁹F,³¹P) spectral data, these compounds are a mixture of two diastereomers with a ratio close to the statistical.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1853–1860, August, 1989.     

Catalytic phosphorylation of polyfluoroalkanols

Phosphorylation of α-polyfluoroalkylbenzyl alcohols by an excess of phenylphosphonic dichloride in the presence of Mg or CaCl₂ as the catalyst givesO-(α-polyfluoroalkylbenzyl) phenylphosphonochloridates (63–79% yield). The reaction proceeds stereoselectivity, and the phosphonochloridates obtained are mixtures of two diastereomers with predominance (approximately by 10%) of one of them. For Part 15, see Ref. 1. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1776–1779, September, 1998.     

Catalytic phosphorylation of polyfluoroalkanols. 11. α-Polyfluoroalkylbenzyldichlorophosphates as phosphorylating agents in the catalytic phosphorylation of primary polyfluoroalkanols

Conclusions -Polyfluoroalkylbenzyldichlorophosphates react, in the presence of catalytic quantities of certain metals or their salts, with polyfluorinated primary alcohols with the formation of phosphorylation products [bis(polyfluoroalkyl)(-polyfluoroalkylbenzyl)phosphates] exclusively.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1660–1664, July, 1989.     

Catalytic phosphorylation of polyfluoroalkanols Communication 10. Catalytic phosphorylation of α-polyfluoroalkylbenzyl alcohols by diaryl chlorophosphates

Conclusions Irrespective of the structure of the alcohol and the reaction conditions, catalytic phosphorylation of -polyfluoroalkylbenzyl alcohols by diaryl chlorophosphates leads exclusively to -polyfluoroalkylbenzyl diaryl phosphates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 878–882, April, 1985.     

Silica gel supported phosphonium salts as micellar and phase transfer catalysts

Phosphonium salts immobilized on silica gel have been found to be both micellar and phase-transfer catalysts. They are able to exchange their parent anions with the anions present in an aqueous solution and promote, in catalytic amounts, the decarboxylation of 6-nitrobenzisoxazole-3-carboxylate to give 2-cyano-5-nitrophenolate, a test for micellar catalysis.     

Catalytic phosphorylation of polyfluoroalkanols. 15. Catalytic phosphorylation of α-polyfluoroalkylbenzyl alcohols by bis(polyfluoroalkyl) chlorophosphates

The catalytic phosphorylation of -polyfluoroalkylbenzyl alcohols by bis(polyfluoroalkyl) chlorophosphates is a convenient method for the synthesis of various bis(polyfluoroalkyl)(-polyfluoroalkylbenzyl) phosphates, including those having donor substituents in the benzene ring. It was shown that in the series of p-methyl--trifluoromethylbenzyl phosphates p-CH₃C₆H₄CH-(CF₃)OP(O)XY (where X, Y=Cl, CF₃CH₂O), the ability to act as O-alkylating agents with respect to polyfluorinated alcohols is a common characteristic, and the alkylating ability increases symbatically with increase in the overall electron-acceptor strength of the X and Y substituents at the phosphorus atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 878–886, April, 1990.     

Synthesis of polymer-supported phosphonium salts and their use as phase transfer catalysts

Spacer-modified polymer supports have been synthesized through the polymeric Grignard reagent method. Phosphonium-active sites were then introduced into these supports and the polymer-supported phosphonium salts were used as phase transfer catalysts for the nucleophilic substitution reactions. Influences of organic solvent, properties of the spacer and temperature on the catalytic activity have been investigated. Based on the experimental results, it was assumed that there might exist a dissolubility equilibrium of the catalytic site between the organic phase and the aqueous phase. With this idea, the results have been reasonably elucidated.     

Palladium nanoparticles stabilized by sterically hindered phosphonium salts as Suzuki cross-coupling catalysts

Palladium nanoparticles with an average size of 2.5±0.5 nm formed from palladium acetate in the presence of tri-tert-butyl(decyl)phosphonium tetrafluoroborate without an additional reducing agent exhibit high activity as a catalyst for the Suzuki cross-coupling reaction involving bromo- and chloroarenes under mild conditions.     

Self association of some quaternary ammonium and phosphonium salts in benzene

From the dependence of the molal osmotic coefficients of (hept)₄NX (X = Cl, Br, J), (hept)₄NNO₃ and (oct)₄PNO₃, in benzene at 33, 40 and 50°C, on the solute concentration, the dimerization constants of solute ion-pairs and the corresponding thermodynamic functions of dimerization, ΔG°, ΔH° and ΔS° have been calculated. The thermodynamic data are discussed in terms of a simple electrostatic model of association.     

Methylcarbonate and bicarbonate phosphonium salts as catalysts for the nitroaldol (Henry) reaction

Phosphonium ionic liquids exchanged with bicarbonate and methylcarbonate anions (CILs) exhibit catalytic performances comparable to those of sterically hindered (non nucleophilic) organosuperbases such as DBU. At 25-50 °C, under solventless conditions, CILs efficiently catalyze the Henry addition of different aldehydes and ketones to nitroalkanes: not only they allow the selective formation of nitroaldols but they unlock a novel high-yielding access to dinitromethyl derivatives of ketones.     

Catalytic phosphorylation of polyfluoroalkanols. 14. Synthesis and diastereomeric conversion of aryl(α-polyfluoroalkylbenzyl) chlorophosphates

Aryl(-polyfluoroalkylbenzyl) chlorophosphates are formed upon catalytic phosphorylation of -polyfluoroalkylbenzyl alcohols with excess aryl dichlorophosphates. Reaction stereochemistry is under thermodynamic control; the product aryl(-polyfluoroalkylbenzyl) chlorophosphates consist of equilibrium mixtures of diastereomers with a statistical (11) ratio of components. Diastereomeric interconversions of aryl(-polyfluoroalkylbenzyl) chlorophosphates occur both in the melt (or in solution) as well as in the crystalline state, but in opposite direction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 433–441, February, 1990.     

Synthesis of bismuth complexes from bismuth iodide and ammonium and phosphonium salts

The complexes [Et₂NH₂] ₃ ⁺ [BiCl₆]^3? (I), [NH₄]⁺[BiI₄(C₅H₅N)₂]^?·2C₅H₅N (II), [Ph₃MeP] ₂ ⁺ [BiI₅]^2? (III), [Ph₃MeP] ₂ ⁺ [BiI₅(C₅H₅N)]^2?·C₅H₅N (IV), [Ph₃MeP] ₃ ⁺ [Bi₃I₁₂]^3? (V), [Ph₃(i-Pr)P] ₃ ⁺ [Bi₃I₁₂]^3?·2Me₂C=O (VI), [Ph₃BuP] ₂ ⁺ [Bi₂I₈·₂Me₂C=O]^2? (VII), and [Ph₃BuP] ₂ ⁺ [Bi₂I₈·2Me₂S=O]^2? (VIII) were obtained by reactions of bismuth iodide with ammonium and phosphonium iodides in acetone, pyridine, or dimethyl sulfoxide.     

Reactions of bismuth iodide with ammonium,phosphonium, and bismuthonium salts

The reactions of ammonium, phosphonium, and bismuthonium salts with bismuth iodide were used to synthesize a series of complex compounds with bismuth-containing anions: [(HOC₂H₄)₃NH]⁺ ₄[Bi₄I₁₆]^4?, [Ph₃EtP] ₃ ⁺ [Bi₂I₉]^3?, and [Ph₄Bi] ₃ ⁺ [Bi₅I₁₈]^3?. X-ray diffraction data show that the nitrogen atoms in the two types of crystallographically independent cations of the nitrogen-containing complex possess a distorted tetrahedral coordination [the CNC angles are 110.3(9)°–113.2(9)°]. In the tetranuclear centrosymmetric [Bi₄I₁₆]^4? anion, the bismuth atoms have an octahedral coordination: Two types of groups, BiI₂ and BiI₃, are bound with one another by four μ₂-and two μ₃-iodine bridges (the Bi-I-μ₂, Bi-I-μ₃, and Bi-I-μ₁ distances are 3.1296(10), 3.2808(8); 3.3210(8) and 2.8670(8)–2.9108(9) Å, respectively). The coordination of the phosphorus atom in the [Ph₃EtP]⁺ cations of the phosphorus-containing complex is close to tetrahedral (the CPC angles are 107.5°–114.1°). In the binuclear [Bi₂I₉]^3? anions, the bismuth atoms have an octahedral coordination. The axial I-Bi-I angles are 167.52(2)°, 169.84(2)°, and 174.97(2)°. The terminal BiI₃ fragments [Bi²-I^7,8,9 2.9238(7), 2.9236(7), and 2.9522(7) Å] are in the eclipsed conformation.     

Induction of thermotropic bicontinuous cubic phases in liquid-crystalline ammonium and phosphonium salts

Two series of wedge-shaped onium salts, one ammonium and the other phosphonium, having 3,4,5-tris(alkyloxy)benzyl moieties, exhibit thermotropic bicontinuous "gyroid" cubic (Cub(bi)) and hexagonal columnar liquid-crystalline (LC) phases by nanosegregation between ionophilic and ionophobic parts. The alkyl chain lengths on the cationic moieties, anion species, and alkyl chain lengths on the benzyl moieties have crucial effects on their thermotropic phase behavior. For example, triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium hexafluorophosphate forms the thermotropic Ia3d Cub(bi) LC phase, whereas an analogous compound with trifluoromethanesulfonate anion shows no LC properties. Synchrotron small-angle diffraction intensities from the Ia3d Cub(bi) LC materials provide electron density maps in the bulk state. The resulting maps show convincingly that the Ia3d Cub(bi) structure is composed of three-dimensionally interconnected ion nanochannel networks surrounded by aliphatic domains. A novel differential mapping technique has been applied successfully. The map of triethyl-[3,4,5-tris(decyloxy)benzyl]ammonium tetrafluoroborate has been subtracted from that of the analogous ammonium salt with hexafluorophosphate anion in the Ia3d Cub(bi) phases. The differential map shows that the counteranions are located in the core of the three-dimensionally interconnected nanochannel networks. Changing from trimethyl- via triethyl- to tripropylammonium cation changes the phase from columnar to Cub(bi) to no mesophase, respectively. This sensitivity to the widened shape for the narrow end of the molecule is explained successfully by the previously proposed semiquantitative geometric model based on the radial distribution of volume in wedge-shaped molecules. The LC onium salts dissolve lithium tetrafluoroborate without losing the Ia3d Cub(bi) LC phase. The Cub(bi) LC materials exhibit efficient ion-transporting behavior as a result of their 3D interconnected ion nanochannel networks. The Ia3d Cub(bi) LC material formed by triethyl-[3,4,5-tris(decyloxy)benzyl]phosphonium tetrafluoroborate shows ionic conductivities higher than the analogous Ia3d Cub(bi) material based on ammonium salts. The present study indicates great potential of Cub(bi) LC nanostructures consisting of ionic molecules for development of transportation nanochannel materials.     

Catalytic activity of various Lewis acids in the phosphorylation of primary polyfluoroalkanols with phosphoryl chloride

The catalytic activity of SnCl₂, SnCl₄, SbCl₃, SbCl₅, and BiCl₃ in the reaction of 2,2,3,3,4,4,4-heptafluoroubutanol with POCl₃ was studied. The mechanism of this reaction is discussed. Strong Lewis acids were found to be less active catalysts. On 90th birthday of Academician M. I. Kabachnik. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2070–2071, October, 1998.     

Nano-biphasic ionic liquid systems composed of hydrophobic phosphonium salts and a hydrophilic ammonium salt

A combination of a phosphonium-type-zwitterions-lithium bis(trifluoromethanesulfonyl)imide complex and a hydrophilic ammonium salt provides a nanosegregated liquid-crystalline matrix consisting of hydrophilic ionic liquid (IL) domains and hydrophobic IL domains.     

Polymeric phosphonium salts as a novel class of cationic biocides. IV. Synthesis and antibacterial activity of polymers with phosphonium salts in the main chain

Polymers with phosphonium salts and different alkyl spacers in the main chain were prepared, and their antibacterial activities against Staphylococcus aureus and Escherichia coli were explored by the viable cell counting method in sterile distilled water. The antibacterial activity of the polymers was found to be higher than that of the corresponding model compounds against each strain, and the effect of the molecular weight on the antibacterial activity was also observed for the compounds with the same spacer length. The antibacterial activity of the polymer samples bonded with different spacer lengths was found to increase with increasing the spacer length against both strains. © 1993 John Wiley & Sons, Inc.