Mono and Bisphosphonates from Perfluoro Olefins and Polyfunctional Fluoro Ketones. Syntheses, Molecular Structure and Derivatives

Perfluoroalkenyl phosphonates were formed along with Me3SiF using CF3CF=CF2, CF3CH=CF2, F5SCF=CF2 or F5SCH=CF2 and silylated phosphites, (R1O)2POSiMe3 (R1=Et, SiMe3). This straightforward method could be extended to perfluorobutadienes CF2=C(RF)C(RF)=CF2 (RF F=F, CF3). The formation of CF3C(=O)P(=O)(OSiMe3)2 and further reactions to yield bisphosphonates will be described. Acetylphosphonates, R2C(=O)P(=O)(OSiMe3)2 (R2=CH3, CF3) reacted with the ketimine, CH3C(=NiPr)Ph to give α-hydroxy-γ-imino phosphonates. Trifluoroacetylphenol and 2,6-bis(trifluoracetyl)-4-methyl-phenol have been proven to be versatile precursors for α-and γ-hydroxy phosphonates. Intermediates in these reactions were found to be cyclic λ5σ5P species.