Donald J. Burton, Ryutaro Takei, S. Shin-Ya
1981
Citations
0
Influential Citations
47
Citations
Journal
Journal of Fluorine Chemistry
Abstract
Abstract Diethyl bromodifluoromethyl phosphonate reacts readily with cadmium metal to form a stable cadmium complex. Depending on solvent, this functionalized organocadmium reagent exhibits stability for days to months. It reacts with a variety of electrophiles and serves as a synthetically useful source for the introduction of the difluoromethylene phosphonate group into organic compounds. The synthetic utility of a wide variety of fluoromethylene phosphonium ylides has been a major effort in our laboratory over the past several years [1]. The generation and capture of difluoromethylene ylides ( 1 ) as a general route to difluoromethylene olefins has been of especial interest to us [2]. In an effort to increase the nucleophilicity of the ylide, we have attempted to prepare the analogous phosphonate ylide ( 2 ). Although we have achieved modest success [3] by insitu capture of ( 2 ) in the reaction of sodium dialkyl phosphites with diethyl bromodifluoromethylphosphonate ( 3 ), attempts to pregenerate ( 2 ), either from diethyl difluoromethylphosphonate ( 4 ) or ( 3 ), have met with little success. ( 2 ) appears to have minimal stability even at low temperatures, and scale up processes of synthetic value would seem to be difficult.