Suicide nucleophilic attack: reactions of benzohydroxamate anion with bis(2,4-dinitrophenyl) phosphate
| Autor: | Pedro L. F. da Silva, Haidi D. Fiedler, Faruk Nome, Humberto M. S. Milagre, Marcos N. Eberlin, Elisa S. Orth, Clifford A. Bunton, Renata S. Mello |
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| Rok vydání: | 2009 |
| Předmět: |
Anions
Hydroxamic acid Magnetic Resonance Spectroscopy Molecular Structure Chemistry Organic Chemistry Benzene Nuclear magnetic resonance spectroscopy Hydroxamic Acids Medicinal chemistry Chemical reaction Phosphates chemistry.chemical_compound Kinetics Aniline Nucleophile Lossen rearrangement Organic chemistry Molecule 2 4-Dinitrophenol |
| Zdroj: | The Journal of organic chemistry. 74(14) |
| ISSN: | 1520-6904 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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