666-23-9Relevant 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.
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.
