Solvolysis of Tris-p-nitrophenyl-phosphate in aqueous and reverse micelles

摘要: Abstract The widespread use of toxic phosphates and phosphonates as insecticides, their chemical weapons, has led to investigation fast detoxification decontamination methods. Micelles, microemulsions, cyclodextrines liposomes have been used accelerate phosphate ester decomposition by nucleophiles. Here, hydrolysis, methanolysis hexanolysis Tris-p-nitrophenyl (TNPP), a model for reactive esters, were studied in homogeneous phase, aqueous reverse micelles. Kinetic micellar effects quantitatively analyzed using pseudo-phase models. TNPP hydrolysis was catalyzed cetyltrimethylammonium chloride (CTAC), bromide (CTAB), hexadecylammonium propanesulfonate (HPS), micelles factors five, CTAC, three, CTAB, HPS, respectively. calculated rate constants spontaneous acetate-catalyzed the phase significantly higher than those phase. While water methanol effect acetate cation negligible, catalytic efficiency depended on nature with K+ salt being ca. 20 times more efficient tetraethylammonium non-polar solvents. Sodium dodecylsulfate, SDS, inhibited factor eigth. Reverse CTAB n-hexanol/isooctane (10:90, v/v) did not catalyze but changed bis-p-nitrophenyl phosphate/hexyl-bis-p-nitrophenylphosphate product ratio depending concentration water/detergent ratio.