title: Suicide nucleophilic attack: reactions of benzohydroxamate anion with bis(2,4-dinitrophenyl) phosphate.
abstract: 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.
authors.affiliation: Departamento de Química, Universidade Federal de Santa Catarina, 88040-900 Florianópolis, SC, Brazil.
authors.forename: Elisa S
authors.initials: ES
authors.lastname: Orth
authors.forename: Pedro L F
authors.initials: PL
authors.lastname: da Silva
authors.forename: Renata S
authors.initials: RS
authors.lastname: Mello
authors.forename: Clifford A
authors.initials: CA
authors.lastname: Bunton
authors.forename: Humberto M S
authors.initials: HM
authors.lastname: Milagre
authors.forename: Marcos N
authors.initials: MN
authors.lastname: Eberlin
authors.forename: Haidi D
authors.initials: HD
authors.lastname: Fiedler
authors.forename: Faruk
authors.initials: F
authors.lastname: Nome
mesh_terms: D019297:2,4-Dinitrophenol / Q000737:chemistry*; D000838:Anions; D001554:Benzene; D006877:Hydroxamic Acids / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010710:Phosphates / Q000737:chemistry*
chemical_list: D000838:Anions; D006877:Hydroxamic Acids; D010710:Phosphates; D001554:Benzene; D019297:2,4-Dinitrophenol