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Suicide Nucleophilic Attack: Reactions of Benzohydroxamate Anion with Bis(2,4-dinitrophenyl) Phosphate

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journal contribution
posted on 17.07.2009, 00:00 by Elisa S. Orth, Pedro L. F. da Silva, Renata S. Mello, Clifford A. Bunton, Humberto M. S. Milagre, Marcos N. Eberlin, Haidi D. Fiedler, Faruk Nome
The reaction between the benzohydroxamate anion (BHO) and bis(2,4-dinitrophenyl)phosphate (BDNPP) has been examined kinetically, and the products were characterized by mass and NMR spectroscopy. The nucleophilic attack of BHO follows two reaction paths: (i) at phosphorus, giving an unstable intermediate that undergoes a Lossen rearrangement to phenyl isocyanate, aniline, diphenylurea, and O-phenylcarbamyl benzohydroxamate; and (ii) on the aromatic carbon, giving an intermediate that was detected but slowly decomposes to aniline and 2,4-dinitrophenol. Thus, the benzohydroxamate anion can be considered a self-destructive molecular scissor since it reacts and loses its nucleophilic ability.