The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid
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(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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Journal of Organic Chemistry, v. 74, n. 21, p. 8254-8260, 2009.
