2-CYANOETHYL AND P-NITROPHENETHYL ALPHA-HYDROXYIMINO-PHOSPHONATE AND ALPHA-METHOXYIMINO-PHOSPHONATE - POTENTIAL PRECURSORS OF METAPHOSPHATEANION

Methyl benzoylphosphonochloridate 3 reacted with 2-cyanoethanol or p-n itrophenethyl alcohol to yield methyl 2-cyanoethyl benzoylphosphonate 4a or methyl p-nitrophenethyl benzoylphosphonate 4b. Ketones 4a and 4b were converted into the corresponding oximes, 5a and 5b as a mixture of E and Z isomers, by hydroxylamine: Grimes 5a and 5b were demethylat ed by treatment with sodium iodide or lithium bromide to give the corr esponding monester monosalts 6a and 6b. Reaction of lithium 2-cyanoeth yl or p-nitrophenethyl benzoylphosphonate with methoxylamine afforded the respective oxime methyl ether salts 8a and 8b as predominantly E i somers. Base treatment of 6a and 6b caused their dealkylation to the a nion of alpha-hydroxyiminobenzylphosphonic acid 9 which did not decomp ose further. In contrast, 8a and 8b in aqueous base gave the dianion o f alpha-methoxyaminobenzylphosphonic acid 10, which slowly fragmented to benzonitrile and phosporic acid. The fragmentation is interpreted i n terms of a dissociative mechanism involving the formation of metapho sphate anion.