Artículo de revista
Micellar Effects upon Phosphorylation and Phosphate Ester Hydrolysis
Fecha
1969Registro en:
Journal of the American Chemical Society, Volumen 91, Issue 17, 2018, Pages 4813-4819
15205126
00027863
10.1021/ja01045a040
Autor
Bunton, C. A.
Robinson, L.
Sepulveda, L.
Institución
Resumen
The reactions between hydroxide or fluoride ion and p-nitrophenyl diphenyl phosphate, catalyzed by micelles of cetyltrimethylammonium bromide, are inhibited by phenyl, diphenyl, and p-t-butylphenyl phosphate. With decreasing pH the reaction with hydroxide ion becomes unimportant, and micellar-catalyzed reactions between the substrate and inorganic phosphate ions and phenyl and p-t-butylphenyl phosphate dianions can be observed. Diphenyl phosphate monoanion is unreactive. For the micellar catalyzed reaction the reactivity sequence is t-BuC6H4OPO3 2 > C6H5OPO3 2 > HOP4 2- and depends upon the nonbonding interactions between the cationic micelle and the nucleophilic anion, rather than their inherent nucleophilicities. The second-order rate constants for the micellar-catalyzed reaction with hydroxide ion agree well with those calculated at low pH in borate buffer. © 1969, American Chemical Society. All rights reserved.