666-23-9Relevant academic research and scientific papers
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.
TRANSFORMATIONS OF DIFLUOROPHOSPHINES: THE INFLUENCE OF SOLVENT ON THE REACTION PATHWAY AND RING SIZE IN CYCLOPOLYPHOSPHINES
Schmutzler, Reinhard,Heuer, Lutz,Schomburg, Dietmar
, p. 149 - 156 (2007/10/02)
The spontaneous transformation reactions of some difluorophosphines in chloroform as solvent are described.First, the redox disproportionation of 2,5-dimethylphenyldifluorophosphine, 1, unexpectedly led to the formation of the cyclopolyphosphine, hexakis-(2,5-dimethylphenyl)cyclohexaphosphine, 2a and 2,5-dimethylphenyltetrafluorophosphorane, 3.Secondly, CF3PF2, 4, was found to undergo a scrambling reaction with formation of (CF3)2PF, 5 and PF3, 6, rather than a redox disproportionation.In contrast, the difluorophosphines, RPF2 with R = 2,4,6-trimethylphenyl,9-anthracenyl, and 9-phenanthryl were found to be stable with regard to such transformations.A single crystal X-ray diffraction study of 2 (as a 1:1 solvate with CDCl3, 2a) was conducted. 2 was found to exist in a chair conformation with a PP bond length of 222.9 pm.The previously known hexamer, (PhP)6, 2b, was formed in the redox disproportionation of a neat sample of PhPF2, held at -20 deg C for several months.Its X-ray crystal structure, first reported in 1965, was redetermined, and served to establish the nature of the product. 2b was found to display a conformation very similar to that of 2/2a.Key words: Difluorophosphines; redox disproportionation; cyclopolyphosphines; X-ray crystal structure.
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.
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.
