2071-21-8Relevant articles and documents
Di(hydroperoxy)alkane Adducts of Phosphine Oxides: Safe, Solid, Stoichiometric, and Soluble Oxidizing Agents
Ahn, Shin Hye,Bhuvanesh, Nattamai,Blümel, Janet
, p. 16998 - 17009 (2017)
The di(hydroperoxy)alkane adducts of phosphine oxides 1–9, Ph3PO?(HOO)2CMe2, Cy3PO?(HOO)2CMe2, Ph3PO? (HOO)2CMeEt, Cy3PO?(HOO)2CMeEt, Cy3PO?(HOO)2CEt2, Cy3PO? (HOO)2C(CH2)5, Cy3PO?(HOO)2CMePh, (Ph2P(O)CH2CH2P(O)Ph2)? ((HOO)2CEt2)2, and Ph2P(O)CH2P(O)Ph2?(HOO)2CMe2, respectively, are synthesized and fully characterized by 1H, 13C, and 31P NMR, and IR spectroscopies. Single crystal X-ray structures are reported for 3–9. Different one-pot synthetic pathways, starting from R3P, R3PO, R3PO?H2O, and R3PO?H2O2 are explored and discussed and a mechanism for the formation of the di(hydroperoxy)alkane adducts of phosphine oxides is suggested. The longevity of the adducts is tested by monitoring the oxidation of Ph3P with quantitative NMR. The solubilities of the adducts in organic solvents are presented, and their applicability as stoichiometric oxidizing agents for the selective oxidation of sulfides to sulfoxides is reported.
Rhodium hydride complexes with phosphite/phosphito ligands: syntheses, reactions with isocyanates and the X-ray crystal structure of HRh2H>2(PPh2Me)
Varshney, Ashima,Gray, Gary M.
, p. 415 - 429 (1990)
The recently reported complex, HRh2H>2(CO), is interest because it contains both a metal hydride and an acidic proton.The carbonyl ligand in this complex is readily displaced by P-donor ligands.The bridging protons in the phosphite/phospito ligands can be replaced by BF2 groups.These complexes do not react with carbondioxide or carbon disulfide at room temperature and pressure, but the carbonyl complexes react with isocyanates to yield ureas and oligomers of the isocyanates.The major P-containing compound isolated from these reactions is 2H>3>.The reaction of HRh2BF2>2(CO) with isocyanates gives a complex mixture of P-containing products in which cleavage of the P-O-B bond has occurred.The X-ray crystal structure of HRh2H>2(PPh2Me) is also reported.The complex crystallizes in the orthorhombic space group Pna21 (a 19.523(1), b 13.510(1), c 12.353(3) Angstroem, V 3259.1 Angstroem3, Z = 4).The complex exhibits a distorted octahedral structure with the Rh displaced out of the plane of the phosphite/phosphito ligands toward the PPh2Me ligand.The two phosphite/phosphito chelate rings in this complex are quite different with one planar and the other significantly distorted from a plane.This appears to be due to the different orientations of the phenyl groups of the PPh2Me ligand.
Synthesis, structure and optical features of single adamantanoid Hg-SePh-X anionic clusters stabilized by octahedral complexes (Ph = phenyl; X = Cl, Br, I)
Stieler, Rafael,Bublitz, Fabricio,Schulz Lang, Ernesto,Manzoni De Oliveira, Gelson
, p. 596 - 600 (2012)
The ligand dppmo2 [CH2{P(O)Ph2} 2] (Ph = phenyl), MgCl2·6H2O, MgBr 2, MgI2, FeBr2, CoBr2, NiBr 2 and Hg(SePh)2 react one at
31P NMR spectroscopic analysis on photooxidation of 1,n-bis(diphenylphosphino)alkanes with the aid of DFT calculations
Yasui, Shinro,Yamazaki, Shoko
, (2020/02/15)
The chloroform-d solution of diphosphine, 1,n-bis(diphenylphosphino)alkane (Ph2P(CH2)nPPh2; n = 1-6), was photolyzed with light from a xenon lamp in air. The progress of the reaction was followed by 31P NMR spectroscopy. The observed spectral change showed that the diphosphine is initially oxidized to diphosphine monoxide, Ph2P(═O)(CH2)nPPh2, which is further oxidized to diphosphine dioxide, Ph2P(═O)(CH2)nP(═O)Ph2. The oxidation of the diphosphine to the diphosphine monoxide took place according to first-order kinetics with respect to the concentration of the diphosphine, the first-order rate constant, kobs, being larger with increasing number of the methylene units in the spacer. The observation in kinetics is interpreted based on the conformation of the diphosphine radical cation intermediate initially generated by electron transfer from the photoexcited diphosphine to oxygen. Density functional theory (DFT) calculations predict that the diphosphine radical cation takes “folded” conformation where two phosphorus atoms are arranged closely to each other. The “folded” conformer of the diphosphine radical cation results from electrostatic interaction of these two phosphorus atoms. This conformer explains the observed dependency of kobs on the length of the spacer in the diphosphine.
The development of a new approach toward lanthanide-based OLED fabrication: new host materials for Tb-based emitters
Aslandukov, Andrey N.,Utochnikova, Valentina V.,Goriachiy, Dmitry O.,Vashchenko, Andrey A.,Tsymbarenko, Dmitry M.,Hoffmann, Michael,Pietraszkiewicz, Marek,Kuzmina, Natalia P.
, p. 16350 - 16357 (2018/11/27)
To develop the recently proposed approach toward host selection for lanthanide-based emitters, four phosphine oxides PO = PO1-PO4 were investigated which are able to both increase the electron mobility and to sensitize terbium luminescence. New highly sol
Rh(III)-Catalyzed Phosphine Oxide Migration Reactions: Selective Synthesis of 3-Phosphinoylindoles
Wang, Chun-Hai,Yang, Shang-Dong
supporting information, p. 2401 - 2404 (2018/09/10)
3-Phosphinoylindoles are important components of biological active natural products and materials in pharmaceuticals. Herein, a new approach for the synthesis of 3-phosphinoylindoles has been established by a Rh(III)-catalyzed cyclization from readily acc
Reaction of (2-methoxyprop-2-yl)diphenylphosphine oxide with alkyl bromides
Morgalyuk, Vasilii P.,Strelkova, Tatyana V.,Kagramanov, Nikolai D.,Artem'ev, Alexander V.,Brel, Valery K.
, p. 290 - 291 (2018/06/01)
Treatment of (2-methoxyprop-2-yl)diphenylphosphine oxide with alkyl bromides affords alkyl(diphenyl)phosphine oxides in good yields.
Synthesis of novel phosphonium betaines and bis-betaines derived from hexafluoro-1,4-naphthoquinone
Zhivetyeva,Tretyakov,Bagryanskaya, I.Yu.
, p. 19 - 28 (2017/12/15)
Reactions of hexafluoro-1,4-naphthoquinone with phosphorus-centered bis-phenylphosphanes with structure Ph2P(CH2)nPPh2 (where n = 1–5) and Et2P(CH2)2PEt2 in various solvents (anhydrous C6H6, aq. C6H6, aq. dioxane, aq. DMSO, or MeOH) were investigated. It was shown that the use of aqueous dioxane and DMSO leads to target products of phosphanodefluorination (i.e., phosphorus-containing betaines and bis-betaines) with high yields. We found that the betaines upon purification by thin-layer chromatography underwent various transformations such as a ring contraction (thus yielding novel polyfluorinated indenones) or addition of an acetone molecule at the C[dbnd]O bond of the fluorinated 1,4-naphthoquinone. According to X-ray diffraction analysis, there were intermolecular F?π interactions in the crystal packing of all the obtained betaines. The interactions are characterized by short distances F?Cg from 3.151(5) to 3.831(2) ? (where Cg is a centroid of π-system).
New synthesis of trimethylsilyl diphenylphosphinite
Morgalyuk, Vasily P.,Strelkova, Tat'yana V.,Nifant'ev, Eduard E.,Brel, Valery K.
, p. 397 - 398 (2016/10/05)
Treatment of (2-hydroxyprop-2-yl)diphenylphosphine oxide with silylating agents affords trimethylsilyl diphenylphos-phinite in high yield.
The behaviour of Bis(diphenylphosphino)alkanes towards different active centres
Ewies, Ewies F.,El-Sayed, Naglaa F.,Boulos, Leila S.
, p. 417 - 421 (2016/07/19)
Benzophenones (diarylmethanones) are important starting materials in the synthesis and preparation of organic compounds such as heat-resistant resins, various drugs, and natural products.1-7 1,1′-(Azodicarbonyl)dipiperidine has different pharmacological and biological activities.8-13 The versatility of isatin (1H-indole-2,3-dione) in synthetic organic chemistry is shown in its biological and pharmacological properties and its extensive use in organic synthesis.14 Moreover, quinoxaline 1,4-di-N-oxide is a building block that has a broad range of biological applications.15 Bis(diphenylphosphino)alkanes have been reported as anticancer agents.16-20The useful applications of these starting materials, coupled with our interest in organophosphorus chemistry,21-25 encouraged us to synthesise new organophosphorus compounds and to identify the preferred site of attack of these compounds. We sought to obtain the target compounds by reacting bis(diphenylphosphino) alkanes 1a-c with some different organic compounds; namely, benzophenone2, 1,1′-(azodicarbonyl)dipiperidine (ADDP, 3), isatin 4a and 4b, and quinoxaline 1,4-di-N-oxide 5 (Scheme 1).
