1868-53-7Relevant articles and documents
THE HYDROLYSIS OF DIBROMOFLUOROMETHYLTRIPHENYLPHOSPHONIUM BROMIDE
Burton, Donald J.,Flynn, R. M.,Manning, R. G.,Kessler, R. M.
, p. 371 - 376 (1982)
Hydrolysis of Br(1-) afforded a high yield of dibromofluoromethane and triphenylphosphine oxide.Hydrolysis in the presence of a radioactive isotope of bromine gave evidence that the mechanism of this reaction proceeds via the dibromofluoromethide ion and not via a bromofluorocarbene intermediate.
Synthetic and mechanistic aspects of halo-F-methylphosphonates
Flynn, Richard M.,Burton, Donald J.
experimental part, p. 815 - 828 (2011/10/08)
The synthesis of a variety of new halo-F-methylphosphonates has been achieved by a Michaelis-Arbuzov type reaction between a halo-F-methane and a trialkyl phosphite. This synthesis has proved to be of wide scope and utility for the high yield preparation of a number of heretofore unknown compounds. The 1H, 19F, 13C and 31P NMR spectroscopic properties are reported in detail. The mechanism for the formation of bromodifluoromethylphosphonates has been shown to proceed through the intermediacy of difluorocarbene:CF2. The phosphonate products have been shown to react with a wide variety of reagents. Fluoride and alkoxide ions react by attack at phosphorus with cleavage of the carbon-phosphorus bond and formation of [:CF2] from the bromodifluoromethylphosphonates and the CFBr2- anion from the dibromofluoromethylphosphonates. Iodide ion and tertiary phosphines react by attack at the ester carbon to give stable phosphonate salts. Hydrolysis of the phosphonate esters with 50% aqueous HCl gives the expected phosphonic acids. Trimethylsilyl bromide attacks phosphoryl oxygen to afford the bis(trimethylsilyl) esters.
PREPARATION OF HALO-F-METHANES VIA POTASSIUM FLUORIDE-HALOGEN CLEAVAGE OF HALO-F-METHYLPHOSPHONIUM SALTS
Burton, D. J.,Shin-Ya, S.,Kesling, H.S.
, p. 89 - 98 (2007/10/02)
Treatment of halo-F-methylphosphonium salts with potassium fluoride and halogen (I2, Br2, ICl, IBr) gives modest yields of halo-F-methanes.This method of preparation augments the classical Hunsdiecker approach to these materials.