683-19-2Relevant academic research and scientific papers
Selective Substitution of POCl 3 with Organometallic Reagents: Synthesis of Phosphinates and Phosphonates
Verbelen, Bram,Dehaen, Wim,Binnemans, Koen
, p. 2019 - 2026 (2018/04/14)
The selectivity of the substitution reaction of phosphoryl chloride with organometallic reagents was investigated using NMR spectroscopy. This led to the discovery that the selectivity of the substitution reaction can be tuned by choosing a proper organometallic reagent. A phosphinate could be obtained by using a Grignard reagent whereas an organozinc reagent provided a phosphonate. Based on these results, one-pot synthetic methods for the preparation of phosphinates and phosphonates using commercially available starting materials were developed. Both methods allow the synthesis of a broad range of either phosphinate or phosphonate derivatives in a straightforward and general procedure. Moreover, using these one-pot procedures, mixed systems substituted with different alkyl/aryl groups can be prepared.
UV-mediated hydrophosphinylation of unactivated alkenes with phosphinates under batch and flow conditions
Gelat, Fabien,Roger, Maxime,Penverne, Christophe,Mazzad, Ahmed,Rolando, Christian,Chausset-Boissarie, La?titia
, p. 8385 - 8392 (2018/03/09)
A UV-mediated hydrophosphinylation of unactivated alkenes with H-phosphinates and hypophosphorous acid under radical free conditions is presented. The reaction affords selectively a large number of structurally diverse organophosphorous compounds in moderate to good yields under mild reaction conditions in the presence of an organic sensitizer as catalyst irradiated by UV-A LEDs. Furthermore, the high yielding hydrophosphinylation in continuous flow is disclosed.
Microwave-assisted synthesis of dialkylphosphinic acids and a structure-reactivity study in rare earth metal extraction
Du, Ruo-Bing,An, Huaying,Zhang, Suhui,Yu, Donghai,Xiao, Ji-Chang
, p. 104258 - 104262 (2015/12/24)
Dialkylphosphinic acids were synthesised by a microwave-assisted method with high yields and wide substrate applicability. A structure-reactivity study indicates that an increase in steric hindrance in the β position led to a decrease of extraction ratio and heavy rare earth element separation activity. A computational study was also conducted to understand the steric effect.
Manganese-catalyzed and promoted reactions of H-phosphinate esters
Fisher, Henry C.,Berger, Olivier,Gelat, Fabien,Montchamp, Jean-Luc
supporting information, p. 1199 - 1204 (2014/05/06)
H-Phosphinates react with alkenes and alkynes using catalytic manganese(II) acetate. Under stoichiometric conditions with manganese(III) acetate or with catalytic manganese(II) acetate+excess manganese(II) oxide various reactions like arylation or cyclization through radical oxidative arylation can take place. Whereas the chemistry of manganese is already well developed for the functionalization of H-phosphonates, the present methodology provides an unprecedented access to functionalized phosphinates in acceptable to good yields.
Synthesis of disubstituted phosphinates via palladium-catalyzed hydrophosphinylation of H-phosphinic acids
Petit, Christelle,Fecourt, Fabien,Montchamp, Jean-Luc
, p. 1883 - 1888 (2011/10/04)
The first metal-catalyzed hydrophosphinylation of unsaturated hydrocarbons with H-phosphinic acids is described. A strategy to activate the P-H bond through control of the tautomeric equilibrium using ethylene glycol is described. The reactions also avoid chromatographic purification. Copyright
Spectroscopic identification of tri-n-octylphosphine oxide (TOPO) impurities and elucidation of their roles in cadmium selenide quantum-wire growth
Wang, Fudong,Tang, Rui,Kao, Jeff L.-F.,Dingman, Sean D.,Buhro, William E.
supporting information; experimental part, p. 4983 - 4994 (2009/09/30)
Tri-n-octylphosphine oxide (TOPO) is the most commonly used solvent for the synthesis of colloidal nanocrystals. Here we show that the use of different batches of commercially obtained TOPO solvent introduces significant variability into the outcomes of CdSe quantum-wire syntheses. This irreproducibility is attributed to varying amounts of phosphorus-containing impurities in the different TOPO batches. We employ 31P NMR to identify 10 of the common TOPO impurities. Their beneficial, harmful, or negligible effects on quantum-wire growth are determined. The impurity di-n-octylphosphinic acid (DOPA) is found to be the important beneficial TOPO impurity for the reproducible growth of high-quality CdSe quantum wires. DOPA is shown to beneficially modify precursor reactivity through ligand substitution. The other significant TOPO impurities are ranked according to their abilities to similarly influence precursor reactivity. The results are likely of general relevance to most nanocrystal syntheses conducted in TOPO.
SYNTHESIS OF ACYCLIC AND CYLIC DIALKYLPHOSPHINIC ACIDS FROM AMMONIUM HYPOPHOSPHITE
Kurdyumova, N. R.,Ragulin, V. V.,Tsvetkov, E. N.
, p. 380 - 383 (2007/10/02)
The possibilities of synthesizing dialkylphosphinic and cyclic phosphinic acids from ammonium hypophosphite, hexamethyldisilazane, and corresponding halogen derivatives have been studied.These acids can be prepared in low yield, but the simplicity of the process compensates for this disadvantage.
INVESTIGATION OF THE REACTION BETWEEN DIALKYLPHOSPHINE OXIDES AND CARBONTETRACHLORIDE
Aksnes, Gunnar,Majewski, Piotr
, p. 261 - 274 (2007/10/02)
The time dependent formation of intermediates and end products in the reaction between Et2P(O)H and CCl4 is analysed using (31)P-NMR technique.The various reaction steps are studied separately in order to elucidate the overall mechanism.A key step is the disproportionation of Et2P(O)H catalysed by Et2PCl and Et2P(O)Cl, in a cyclic process, the latter being produced initially by the reaction between Et2P(O)H and CCl4.The diethylphosphine formed during disproportionation reacts immediately with CCl4, driving the reaction through the intermediates, Et2PCl and Et2PCCl3which react with Et2P(O)OH producing Et2P(O)Cl, (Et2PO)2O, and Et2P(O)CHCl2, as end products.The influence of the substituents on rate and product yields was studied with n-propyl, n-butyl, n-octyl, and allyl as substituents in the dialkylphosphine oxide.
