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, ((RO)-O-1)(2) POSiMe3 (R-1 = Et, SiMe3). This straightforward method could be extended to perfluorobutadienes CF2=C(R-F)C(R-F)=CF2 (R-F F=F, CF3). The formation of CF3C(=O)P(=O)(OSiMe3)(2) and further reactions to yield bisphosphonates wil l be described. Acetylphosphonates, (RC)-C-2(=O)P(=O)(OSiMe3)(2) (R-2= CH3, CF3) reacted with the ketimine, CH3C(=NiPr)Rh to give alpha-hydroxy-gamma- imino phosphonates. Trifluoroacetylphenol and 2,6-bis(trifluoracetyl)-4-met hyl-phenol have been proven to be versatile precursors for alpha-and gamma- hydroxy phosphonates. Intermediates in these reactions were found to be cyc lic lambda(5)sigma(5)p species.