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

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• 作者：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
• 刊名：Journal of Organic Chemistry
• 出版年：2009
• 出版时间：July 17, 2009
• 年：2009
• 卷：74
• 期：14
• 页码：5011-5016
• 全文大小：241K
• 年卷期：v.74,no.14(July 17, 2009)
• ISSN：1520-6904

文摘

The reaction between the benzohydroxamate anion (BHO<sup>−sup>) 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<sup>−sup> 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.