Reaction of Bis(2,4-dinitrophenyl) Phosphate with Hydrazine and Hydrogen Peroxide. Comparison of O- and N- Phosphorylation

Abstract

Nonionic hydrazine reacts with anionic bis(2,4-dinitrophenyl) phosphate (BDNPP), giving 2,4-dinitrophenyl hydrazine and dianionic 2,4-dinitrophenyl phosphate by an S(N)2(Ar) reaction, and at the phosphoryl center, giving 2,4-dinitrophenoxide ion and a transient phosphorylated hydrazine that rearranges intramolecularly to N-(2,4-dinitrophenyl)-N-phosphonohydrazine. Approximately 58% of the reaction at pD = 10 occurs by N-phosphorylation, as shown by (31)P NMR spectroscopy. Reaction of HO(2)(-) is wholly at phosphorus, and the intermediate peroxophosphate reacts intramolecularly, displacing a second 2,4-dinitrophenoxide ion, or with H(2)O(2), giving 2,4-dinitrophenyl phosphate and O(2). Rate constants of O- and N-phosphorylation in reactions at phosphorus of NH(2)NH(2), HO(2)(-), and NH(2)OH and its methyl derivatives follow Bronsted relationships with similar slopes, but plots differ for oxygen and nitrogen nucleophiles. The reaction with NH(2)NH(2) has been probed by using both NMR spectroscopy and electrospray ionization mass and tandem mass spectrometry, with the novel interception of key reaction intermediates in the course of reaction.