4141-50-8Relevant academic research and scientific papers
Anomalous reactivity of diphenylhydroxymethylphosphine oxide in the synthesis of a phosphorylated ether by oxa-Michael reaction
Cristau,Virieux
, p. 703 - 706 (1999)
Vinylic phosphorus compounds were found to react as Michael olefins with alcohols in basic catalytic conditions. Several phosphorylated polyethers were obtained in such a way. In analogous conditions, the hydroxymethylphosphine oxide used as alcoholic reagent looses formaldehyde leading to 1,2-diphosphorus compound formation.
Reaction of haloacrylic acids with phosphorus nucleophiles
Khachatryan,Kotikyan,Hachikyan,Panosyan,Mirzakhanyan,Indzhikyan
, p. 1506 - 1510 (2003)
α-Chloroacrylic acid reacts with triphenylphosphine to give (E)-(2-carboxyvinyl)triphenylphosphonium chloride. The same reaction with β-halomethacrylic acids yields, depending on the temperature, either (2-carboxypropenyl)triphenylphosphonium halides or t
A salt-free synthesis of 1,2-bisphosphorylethanes via an efficient PMe3-catalyzed addition of >P(O)H to vinylphosphoryl compounds
Saga, Yuta,Han, Daoqing,Kawaguchi, Shin-Ichi,Ogawa, Akiya,Han, Li-Biao
, p. 5303 - 5305 (2015)
Abstract A convenient and versatile method was developed for the preparation of 1,2-bisphosphorylethanes. Thus, in the presence of a catalytic amount of trimethylphosphine, a variety of >P(O)H compounds efficiently add to vinylphosphoryl compounds to produce the corresponding 1,2-bisphosphorylethanes in high yields. In most cases, the trimethylphosphine catalyst was simply removed under vacuum leaving spectroscopically pure adducts. The present method provided a halogen and metal-free clean process for the preparation of 1,2-bisphosphorylethanes.
Catalytic air oxidation of tertiary arylphosphines in the presence of tin(IV) iodide
Levason, William,Patel, Rina,Reid, Gillian
, p. 280 - 282 (2003)
Arylphosphines including Ph3P, o-C6H4 (PPh2)2 and Ph2PCH2CH 2PPh2 are cleanly and quantitatively converted into the corresponding phosphine oxides on reaction with dry air or dioxygen in CH2Cl2 solution in the presence of catalytic amounts of SnI4.
2-Phenoxyethyldiphenylphosphine oxide as an equivalent of diphenylvinylphosphine oxide in nucleophilic additions
Bondarenko, Natalia A.,Tcarkova, Kseniia V.,Belus', Svetlana K.,Artyushin, Oleg I.
, p. 902 - 910 (2021/06/25)
A facile method for the synthesis of β-functionalized ethyldiphenylphosphine oxides is developed based on readily available 2-phenoxyethyldiphenylphosphine oxide used as an equivalent of diphenylvinylphosphine oxide in the reactions of addition of different PH- and NH-nucleophiles in DMSO in the presence of KOH. The transformations of labile phosphine oxides of a general formula Ph2P(O)CH2CH2OR, where R = Ph, H, or Ph2P(O)CH = CH2, in aq.KOH/DMSO and solid KOH/DMSO systems are explored in the absence of nucleophilic reagents.
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
Novel Bis[N-alkyl-N-(2-diphenylphosphinylethyl)]diglycolamides: Synthesis and NMR Spectroscopy Studies
Bondarenko,Tcarkova,Belus’,Artyushin,Peregudov
, p. 181 - 189 (2021/03/20)
Abstract: Pentadentate bis[N-alkyl-N-(2-diphenylphosphinylethyl)]diglycolamides [Ph2P(O)CH2CH2N(R)· C(O)CH2]2O, where R Me, Bu, Oct, were synthesized by reaction of diglycolyl chloride with N-alkyl-N-(2-diphenylphosphinylethyl)amines Ph2P(O)CH2CH2NHR obtained by reacting diphenyl(2-phenoxyethyl)phosphine oxide with primary alkylamines in DMSO in the presence of an aqueous alkali. Structure of the prepared compounds was studied by 1H, 13C, and 31P NMR spectroscopy.
Air-stable phosphine organocatalysts for the hydroarsination reaction
Leung, Pak-Hing,Li, Yongxin,Pullarkat, Sumod A.,Tay, Wee Shan,Yang, Xiang-Yuan
supporting information, (2020/03/18)
Readily-available triarylphosphines are explored as organocatalysts for the hydroarsination reaction. When compared to transition metal catalysis, phosphine organocatalysis greatly improved solvent compatibility of the hydroarsination of nitrostyrenes. Upon complete conversion, arsine products were isolated in up to 99% yield while up to 48% of the phosphine catalyst was still active. A mechanism was proposed and structure-activity analysis regarding catalyst activity concluded that sterically-bulkier catalysts were effective at minimizing catalyst deactivation.
Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines
Hansen, Line Sofie,Jakobsen, Vibe Boel,McKee, Vickie,McKenzie, Christine J.
, p. 4163 - 4169 (2020/10/12)
The polymeric complex trans-[Ni(acac)2(μ2-dppe)]n·2MeCN {1a, dppe = 1,2-ethylenebis(diphenylphosphine)} is sometimes transiently deposited from the reaction of [Ni(acac)2] with dppe in MeCN prior to its facile onwards air oxidation to final crystallization of a doubly-oxygenated relative, cis-[Ni(acac)2(μ2-dppeO2)]n {2, dppeO2 = 1,2-ethylenebis(diphenylphosphineoxide)}. A similar unsolvated phase of the initial polymer, trans-[Ni(acac)2(μ2-dppe)]n (1b), can be isolated from toluene. The oxidation of dppe by O2 is catalytic and dppeO2 was isolated in close to stoichiometric yields from solutions containing 5 % Ni(acac)2 relative to dppe. The reaction rate slows after a few turnovers due to inhibition by the product. The relative yields of dppeO2 are higher than those from catalytic air oxidation of methyldiphenylphosphine and triphenylphosphine and we speculate that a pathway for this reaction involves a dimetallic cooperativity enabled specifically by dppe.
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.
