Suicide nucleophilic attack: reactions of benzohydroxamate anion with bis(2,4-dinitrophenyl) phosphate.
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.
Orth
Elisa S
ES
Departamento de Química, Universidade Federal de Santa Catarina, 88040-900 Florianópolis, SC, Brazil.
da Silva
Pedro L F
PL
Mello
Renata S
RS
Bunton
Clifford A
CA
Milagre
Humberto M S
HM
Eberlin
Marcos N
MN
Fiedler
Haidi D
HD
Nome
Faruk
F
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*
D000838:Anions; D006877:Hydroxamic Acids; D010710:Phosphates; D001554:Benzene; D019297:2,4-Dinitrophenol