The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid
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2009-11-06
Autores
Silva, Marcelo
Mello, Renata S.
Farrukh, M. Akhyar
Venturini, Janio
Bunton, Clifford A.
Milagre, Humberto M. S. [UNESP]
Eberlin, Marcos N.
Fiedler, Haidi D.
Nome, Faruk
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Resumo
(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.