SYNTHESIS AND CHARACTERIZATION OF (E) AND (Z)-1,2-DIFLUOROETHENEDIYLBISPHOSPHONATES

Article abstract of DOI:10.1016/S0022-1139(00)80364-4

Cuprous halide mediated decomposition of (diethoxyphosphinyl)difluoromethylzinc bromide, (EtO)2P(O)CF2ZnBr, forms the title bisphosphonates in 50percent isolated yield.The 19F and 31P NMR spectra of these isomeric bisphosphonates exhibit non-first order AA'XX' patterns.Computer simulation permitted the determination of the J_P-F, J_F-F, and J_P-P coupling constants for these compounds.Silylation and hydrolysis of the bisphosphonate mixture gave the silylated bisphosphonates and bisphosphonic acids respectively, as expected.Metathesis of the zinc reagent also yielded phenyl (diethoxyphosphinyl)difluoromethylmercury, (EtO)2P(O)CF2HgPh, in good yield.However, attempts to generate fluoro(diethoxyphosphinyl)carbene from this mercurial were unsuccessful.