The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid
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Abstract
(Figure Presented) Mixed micelles of cetyltrimethylammonium bromide (CTABr) or dodecyltrimethylammonium bromide (DTABr) and the α-nucleophile, lauryl hydroxamic acid (LHA) accelerate dephosphorylation of bis(2,4-dinitrophenyl) phosphate (BDNPP) over the pH range 4-10. With a 0.1 mole fraction of LHA in DTABr or CTABr, dephosphorylation of BDNPP is approximately 10 4-fold faster than its spontaneous hydrolysis, and monoanionic LHA - is the reactive species. The results are consistent with a mechanism involving concurrent nucleophilic attack by hydroxamate ion (i) on the aromatic carbon, giving an intermediate that decomposes to undecylamine and 2,4-dinitrophenol, and (ii) at phosphorus, giving an unstable intermediate that undergoes a Lossen rearrangement yielding a series of derivatives including N,N-dialkylurea, undecylamine, undecyl isocyanate, and carbamyl hydroxamate. © 2009 American Chemical Society.
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Aromatic carbon , Cetyltrimethylammonium bromide , Dephosphorylations , Dinitrophenols , Dinitrophenyl , Dodecyltrimethylammonium bromides , Hydroxamate , Hydroxamic acids , Mixed micelles , Mole fraction , Nucleophilic attack , pH range , Reactive species , Spontaneous hydrolysis , Ammonium compounds , Dyes , Micelles , Organic acids , Phenols , Phosphorus , Cationic surfactants , 2,4 dinitrophenol , carbon , cationic surfactant , cetrimide , decylamine , dodecyltrimethylammonium bromide , hydroxamic acid derivative , isocyanic acid derivative , nucleophile , phosphate , phosphorus , urea derivative , concentration (parameters) , dephosphorylation , electrospray mass spectrometry , hydrolysis , ionization , kinetics , mass spectrometry , micelle , micellization , pH , species , Cations , Hydroxamic Acids , Kinetics , Magnetic Resonance Spectroscopy , Phosphoric Acid Esters , Phosphorylation , Potentiometry , Spectrometry, Mass, Electrospray Ionization , Surface-Active Agents
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English
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Journal of Organic Chemistry, v. 74, n. 21, p. 8254-8260, 2009.
