Selective reduction of allenyl(diphenyl)phosphine oxides to allyl(diphenyl)phosphine oxides

The reduction of allenyl(diphenyl)phosphine oxides with HSiCl₃ or LiAlH₄ selectively afforded the corresponding allyl(diphenyl)phosphine oxides. 3-Methylbut-2-en-1-yl(diphenyl)phosphine oxide reacted with AlCl₃ to give a mixture of 4,4-dimethyl-1-phenyl-1,2,3,4-tetrahydro-λ⁵-phosphinoline 1-oxide and 4,4-dimethyl-1-phenyl-1,4-dihydro-λ⁵-phosphinoline 1-oxide.     

Conformational analysis of dimethyl(bromomethyl)- and dimethyl(iodomethyl)phosphine oxides

Conclusions The oxides of dimethyl(bromomethyl)- and dimethyl(iodomethyl)phosphines exist as equilibrium mixtures of conformer pairs in solution, the form predominating in nonpolar solvents being that in which the phosphoryl and carbon-halogen bonds are in trans orientation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1292–1296, June, 1981.     

Extraction of transplutonium elements with diphenyl (alkyl)dialkyl-carbamoylmethyl phosphine oxides

Polydentate neutral organophosphorus compounds attract great interest as efficient extractants of transplutonium elements(TPE) from acid waste nuclear fuel element solution. With the view of a further search, reagents R′R″-PO-CH₂-CNO-R ₂ ^″' were synthetized and investigated. The solubility of R ₂ ^′ POCH₂CNOR ₂ ^″' vas investigated in organic solvents and in nitric acid solutions. This reagent was found to be the best one.     

Study of thermochemical properties of diphenyl[dialkyl(alkyl)carbamoylmethyl]phosphine oxides

The synthesis and the studies of properties of diphenyl[dialkyl(alkyl)carbamoylmethyl]phosphine oxides by differential scanning calorimetry, mass spectrometry and Knudsen effusion method were performed. The thermodynamic parameters of melting and vaporization were calculated.     

Polarity and Conformational Analysis of Tri(1-naphthyl)phosphine,Tri(2-naphthyl)phosphine,and Their Chalcogenides

Russian Journal of Organic Chemistry - The polarity and structure of tri(1- or 2-naphthyl)phosphines and their chalcogenides were determined by the methods of dipole moments, IR spectroscopy, and...     

(Perfluoroalkyl-ethyl) dimethyl phosphine oxides

Phosphine oxidesC_nF_2n+1-C₂H₄-P(O)Me₂, as well as mixtures of the same with C_nF_2n+1-CH Me-P(O)Me₂ are synthesized in two ways. Some of them display outstanding surface activity.     

Ruthenium-catalyzed formation of aryl(diphenyl)phosphine oxides by reactions of propargylic alcohols with diphenylphosphine oxide

1,1-Diaryl-1-penten-4-yn-3-ols react with diphenylphosphine oxide in the presence of a thiolate-bridged diruthenium complex as a catalyst and give high yields of aryl(diphenyl)phosphine oxide products via an initial substitution followed by a cyclization at the produced allene intermediate. [reaction: see text]     

Michael-type addition of secondary phosphine oxides to (1,4-cyclohexadien-3-yl)phosphine oxides

Base-induced reaction between (1,4-cyclohexadien-3-yl)phosphine oxides and secondary phosphine oxides gives 3,4-bis(phosphinoyl)cyclohexenes and 2,3-bis(phosphinoyl)cyclohexenes through an in situ isomerization of one of the cyclohexadienyl double bonds and a subsequent Michael-type addition of the secondary phosphine oxide.     

New trigonal tris(phosphine oxides)

The reaction of 1,1,1-tris(chloromethyl)propane with diphenylphosphine under phase-transfer conditions afforded 1,1,1-tris(diphenylphosphinomethyl)propane, whose oxidation gave a previously unknown representative of trigonal tris(phosphine oxides), viz., stable 1,1,1-tris(diphenylphosphorylmethyl)propane. Its analogs, viz., bis(diphenylphosphoryl)diphenylphosphinomethane and tris(diphenylphosphoryl)methane, are unstable in air and decompose with the cleavage of the P-C bond.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1926–1929, September, 2004.     

双(二苯基膦)烷烃的合成与表征

以三苯基膦为起始原料,四氢呋喃为溶剂,经过金属锂化与烷基化分别合成了1,1-双二苯基膦甲烷(DPPM)、1,2-双二苯基膦乙烷(DPPE)、1,3-双二苯基膦丙烷(DPPP)、1,4-双二苯基膦丁烷(DPPB)、1,5-双二苯基膦戊烷(DPPPe)和1,6-双二苯基膦己烷(DPPH),收率为75%~86%.通过1 H NMR、31 P NMR、MS和元素分析确证了目标化合物的结构.     

Reaction of Pentafluorophenyl(diphenyl)phosphine with Nitrilimines

Reaction of pentafluorophenyl(diphenyl)phosphine with nitrilimines is a multistep process leading to formation of unstable fused heterocycles with a fluorophosphorane moiety as primary products. Their hydrolysis involves opening of the heteroring and subsequent cleavage of the N-N bond in intermediate phosphorylated hydrazones. The final products are diphenyl(6-arylamino-2,3,4,5-tetrafluorophenyl)phosphine oxides.     

Liquid-liquid partition constants of tri-n-octyl,tris (2-ethylhexyl) and triphenyl phosphine oxides

Organic phosphine oxides (S) were determined from γ-counting of ²³⁷U in the 1:1 adduct complex UO₂(TTA)₂ · S (where TTA is thenoyltrifluoroacetone) extracted by synergic effect. Distribution ratios of S are independent of the aqueous pH (1–3) and the reagent concentrations. Partition constants (P_s) were obtained between thirteen organic solvents and aqueous solutions, and they decrease in the order, tri-n-octyl > tris (2-ethylhexyl) > triphenyl phosphine oxides. The P_s values much depend on the kind of solvent, and their regularity is interpreted in terms of solubility parameters.     

Optically active phosphine oxides. 5. P-chiral 2-aminoethyl phosphine oxides

Homochiral 2-aminoethyl phosphine oxides are expeditiously prepared by thermal addition of primary and secondary amines to (−)-(S)-methylphenylvinylphosphine oxide. Their transformation into optically active 2-aminoethyl phosphines and 2-aminoethyl phosphine sulphides is exemplified.     

Microemulsions with alkyldimethyl phosphine oxides and alkyldiethyl phosphine oxides

Alkyldimethyl phosphine oxides (C n DMPO) as well as alkyldiethyl phosphine oxides (C n DEPO) with chain lengths of n = 10 (decyl), 12 (dodecyl), and 14 (tetradecyl) were synthesized and purified to study how the formation of microemulsions depends on the size of the headgroup and on the length of the alkyl chain. For that purpose, equal amounts of water and n-octane were taken and surfactant was added to solubilize the two solvents. The resulting fish-shaped phase diagrams for C 10DEPO, C 12DEPO, and C 14DEPO show that the longer the hydrophobic chain the more efficient the surfactant. Simultaneously, the extension of the lamellar phase (L alpha) shifts toward lower total mass fractions gamma of the surfactant, i.e., the tendency to form lyotropic liquid crystals (LCs) increases. These trends are well-known for nonionic alkyl ethylene oxides and can thus be interpreted accordingly. What is astonishing, however, is the significant influence the size of the short side chains has. Replacing two methyl groups by two ethyl groups leads to a drastic drop of the three-phase region toward lower temperatures, while the efficiency remains nearly unchanged. Moreover, the tendency to form LCs decreases significantly.     

Thermal properties of poly(tertiary phosphine oxides)

DTA and TGA (in air and in nitrogen) are presented for the poly(tertiary phosphine oxides), C₆H₅[(C₆H₅)P(O)CH₂CH₂]_nP(O)(C₆H₅)₂, where n = 1, 2, or 3.     

Efficient one-pot synthesis of diphenyl(pyrazin-2-yl)phosphine and its AgI,AuI and PtII complexes

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Reactions of tris(2-pyridyl)phosphines and tris(2-pyridyl)phosphine oxides with some electrophiles

Treatment of tris(2-pyridyl)phosphine or tris(2-pyridyl)phosphine oxide with electrophiles such as chlorine, bromine, deuterium chloride, or benzenediazonium chloride gave unusual coupling products, i.e., 5-chloro-, 5-bromo-, 5-deuterio-, or 5-phenylazo-2,2′-bipyridyls, respectively, as a major coupling product in each case. This is considered to be the result of electrophilic substitution on a pyridyl ring in a pentacovalent phosphorane intermediate formed in each reaction. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 439–449, 1997     

Neighboring group participation of phosphine oxide functionality in the highly regio- and stereoselective iodohydroxylation of 1,2-allenylic diphenyl phosphine oxides

Two sets of reaction conditions were established to enable the highly regio- and stereoselective iodohydroxylation of 1,2-allenylic diphenyl phosphine oxides, yielding (E)-2-iodo-3-hydroxy-1-alkenyl diphenyl phosphine oxides with very high stereoselectivity. The scope of this reaction was examined extensively. Notably, studies on the reactivity of optically active substrates indicated that the axial chirality in the starting allenes may be efficiently transferred to the center chirality of the products with no discernible loss of enantiopurity. Due to the importance of phosphine-containing compounds, both as reagents and ligands, this reaction shows potentials in organic synthesis. Investigations using ESI-MS technology on the (18)O-labeled product, which was prepared using (18)O-water as the solvent, indicated that the (18)O atom was bound to phosphorus in the final product and the oxygen atom of the hydroxyl comes from the phosphinyl functionality of the allene reactant. These results provided solid evidence for the formation of a five-membered cyclic intermediate from the neighboring group participation of the diphenylphosphinyl group. To the best of our knowledge, this is the first time that the neighboring group participation of this type of group was observed.