Reaction of 1,2-Diaza-1,3-butadienes with Aminophosphorus Nucleophiles: A Practical Access to New Phosphorylated Pyrazolones

The reaction of 1,2-diaza-1,3-butadienes with dibenzyl diisopropylphosphoramidite, methyl tetraisopropylphosphorodiamidite or tris(dimethylamino)phosphane under solvent-free conditions gave stable α-phosphoranylidene-hydrazones that, in turn, were transformed into the corresponding 5-oxo-4-phosphoranylidene-4,5-dihydro-1H-pyrazoles. X-ray diffraction analysis of one of these derivatives is reported. α-Phosphoranylidene-hydrazones, derived from the reaction between 1,2-diaza-1,3-butadienes with dibenzyl diisopropylphosphoramidite, were converted by hydrolytic cleavage into (E)-hydrazono-phosphonates, which are useful for the preparation of the corresponding (3-oxo-2,3-dihydro-1H-pyrazol-4-yl)phosphonamidates.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)