Citation

Orth ES, da Silva PLF, Mello RS, Bunton CA, Milagre HMS, Eberlin MN, Fiedler HD, Nome F. J. Org. Chem. 2009; 74(14): 5011-5016.

Copyright

(Copyright © 2009, American Chemical Society)

DOI

10.1021/jo9007354

PMID

19459594

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.

Language: en

Keywords

2,4-Dinitrophenol; Anions; Benzene; Hydroxamic Acids; Kinetics; Magnetic Resonance Spectroscopy; Molecular Structure; Phosphates