1138-99-4Relevant articles and documents
Deoxygenative Fluorination of Phosphine Oxides: A General Route to Fluorinated Organophosphorus(V) Compounds and Beyond
Bornemann, Dustin,Brüning, Fabian,Grützmacher, Hansj?rg,Guan, Liangyu,Küng, Sebastian,Pitts, Cody Ross,Togni, Antonio,Trapp, Nils,Wettstein, Lionel
supporting information, p. 22790 - 22795 (2020/10/06)
Fluorinated organophosphorus(V) compounds are a very versatile class of compounds, but the synthetic methods available to make them bear the disadvantages of 1) occasional handling of toxic or pyrophoric PIII starting materials and 2) a dependence on hazardous fluorinating reagents such as XeF2. Herein, we present a simple solution and introduce a deoxygenative fluorination (DOF) approach that utilizes easy-to-handle phosphine oxides as starting materials and effectively replaces harsh fluorinating reagents by a combination of oxalyl chloride and potassium fluoride. The reaction has proven to be general, as R3PF2, R2PF3, and RPF4 compounds (as well as various cations and anions derived from these) are accessible in good yields and on up to a multi-gram scale. DFT calculations were used to bolster our observations. Notably, the discovery of this new method led to a convenient synthesis of 1) new difluorophosphonium ions, 2) hexafluorophosphate salts, and 3) fluorinated antimony- and arsenic- compounds.
Preparation method of phosphinate, phosphinate and non-aqueous electrolyte
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Paragraph 0087; 0089, (2020/08/09)
The present invention provides a method for preparing phosphinate, the phosphinate and a non-aqueous electrolyte. The method for preparing the phosphinate comprises the following steps: (1) reaction of Grignard reagent R1MgX with thiophosphoryl halide X3P=S in a solvent to obtain a first intermediate; (2) reaction of halogenating agent M' Xa and the first intermediate to obtian a second intermediate; and (3) reaction of the second intermediate with R2OH and water to obtain the phosphinate; wherein R1 and R2 are each selected from the group consisting of hydrocarbon groups or an organic group containing at least one element of boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine, and iodine; X represents a halogen; M' represents a metal element; and a representsa valence of the metal element M'. The electrolyte prepared by from the phosphinate can improve the high-temperature cycle stability of a secondary battery, also has non-flammable, flame-retardant orself-extinguishing characteristics, and can improve the safety performance of the secondary battery.
Triphenylmethyl fluoride as a fluorinating agent in phosphorus-halogen chemistry
Plack, Volker,Goerlich, Jens R.,Schmutzler, Reinhard
, p. 173 - 176 (2007/10/03)
Triphenylmethyl fluoride 1 will effect chlorine-fluorine exchange in certain phosphorus chlorides. Exchange of chlorine for fluorine was observed only in σ3λ3 (P)- and σ5λ5 (P)-compounds, while phosphorus oxychloride as an example of a σ4λ5 (P)-compound was unreactive towards 1.
THE FLUORINATION OF HYDROPHOSPHORYL COMPOUNDS USING 2-HYDROPERFLUOROPROPYL AZIDE
Lermontov, S. A.,popov, A. V.,Sukhozhenko, I. I.,Pushin, A. N.,Martynov, I. V.
, p. 839 - 841 (2007/10/02)
2-Hydroperfluoropropyl azide efficiently fluorinates hydrophosphoryl compounds to give the corresponding P(V) acid fluorides.
FLUORINATION OF DERIVATIVES OF TRI- AND PENTAVALENT PHOSPHORUS ACIDS BY PERFLUOROPROPYLENE OXIDE
Lermontov, S. A.,Rakov, I. M.,Martynov, I. V.
, p. 2584 - 2587 (2007/10/02)
Perfluoropropylene (I) efficiently fluorinates esters and ester anhydrides of PIII and PV acids to give acid fluoride derivatives of pentavalent phosphorus acids.Phosphites are initially oxidized to the corresponding phosphoryl compounds with subsequent substitution of the oxygen by two fluorine atoms by means of excess oxide (I).
ZUR DISPROPORTIONIERUNG DER PHENYLFLUOROPHOSPHANE (C6H5)2PF UND (C6H5)PF2
Riesel, L.,Haenel, J.,Ohms, G.
, p. 335 - 340 (2007/10/02)
Ph2P-PF2Ph2 has been identified by means of 19F- and 31P-NMR spectroscopy as an intermediate product of the disproportionation of Ph2PF.The disproportionation is catalyzed by acids.The reaction mechanism is discussed.PhPF2 disproportionates faster in solution inacetonitrile that neat, forming (PhP)6, instead of (PhP)5.
CHLOR-FLUOR -AUSTAUSCHREAKTIONEN MIT TRIALKYLFLUOR-PHOSPHORANEN
Bartsch, R.,Schmutzler, R.,Spiegel, G. U.,Stelzer, O.
, p. 107 - 118 (2007/10/02)
Trialkyldifluorophosphoranes R3PF2 (R = iPr, nBu) were found to react with chlorides or organoelement chlorides, EClm or ERm-zClz (EIV, m = 4, z = 1,2; EV, m = 3, z = 1,2) of elements belonging to main groups IV and V with chlorine/fluorine exchange to form the halophosphonium salts +Cl- (X = F, Cl) and the fluoro derivatives, EFm or ERm-zFz.With AlCl3 ionic products of composition are obtained.The transition metal chlorides, NiCl2, PdCl2 NiCl2(PMe3)2, and CoCl2 were found to be less reactive.Chlorine/fluorine exchange has been observed only the case of CoCl2.
BEITRAEGE ZUR CHEMIE DES IODOPENTAFLUORIDS. TEIL IV. IF5 EIN SELEKTIVES OXIDATIVES FLUORIERUNGSMITTEL FUER ORGANOPHOSPHOR(III)-VERBINDUNGEN
Frohn, H. J.,Maurer, H.
, p. 73 - 82 (2007/10/02)
Aryl-and alkylphosphines R3P, R2PF, R2PCl, and RPCl2 are oxidized by IF5 to the corresponding fluorophosphoranes in a fast one step-reaction at or below 0 deg C.The only coproduct is elemental iodine.IF3 or IF as reduction products of IF5 are not observed.Fission of P-C - bonds by from I2 and IF5 is negligible under reaction conditions.In alkylfluorophosphoranes fluoride donor-acceptor-interactions between fluorophosphoranes and IF5 are observed.
