ACYLPHOSPHONAMIDATES AND ALPHA-HYDROXYIMINOPHOSPHONAMIDATES - SYNTHESIS OF N-ACYLPHOSPHORDIAMIDATES BY BECKMANN REARRANGEMENT - CRYSTAL-STRUCTURE OF ALPHA-HYDROXYIMINOBENZYL-1-PYRROLIDINYLPHOSPHINATE

Reaction of methyl benzoylphosphonochloridate (3) with a secondary or primary series of amines yielded methyl benzoylphosphonamidates, 4a-e. The latter compounds reacted with hydroxylamine to yield a-hydroxyimi nobenzylphosphonamidates (5 a-e), largely as (E)-isomers. The structur e of methyl )-a-hydroxyiminoo-benzyl-1-pyrrolidinylphosphinate (5b) wa s determined by single-crystal X-ray crystallography. Heating oximes 5 a-e in boiling toluene caused them to undergo Beckmann rearrangement t o N-benzoylphosphordiamidates 6a-e. (C) 1996 John Wiley & Sons, Inc.