6439-67-4Relevant articles and documents
Enantioselective cleavage of esters by histidine-containing tripeptides in micellar solutions of various hexadecyltrialkylammonium bromide surfactants
Cleij, Marco C.,Drenth, Wiendelt,Nolte, Roeland J. M.
, p. 1 - 6 (2007/10/02)
Cleavage of chiral p-nitrophenyl esters derived from the amino acid phenylalanine by histidine-containing tripeptides has been studied in micellar solutions of four quaternary ammonium surfactants.Enzyme-like enantioselectivities up to kL/kD = 131 (at 0 deg C) are observed.The enantioselectivity can be rationalized by assuming a hydrophobically driven stabilizing hydrogen bond between the L enantiomer of the ester and the tripeptide in the transition state of the reaction.This hydrogen bond is absent in the reaction with the D enantiomer of the ester.The transition state has an amphipolar character and is stabilized by the micellar environment.The hydrophilic-hydrophobic balance of the reactants, which affects the transition state, was optimized by varying the composition of the tripeptide and the length of the N-protecting groups in the tripeptide and the substrate.The activities and enantioselectivities depend on the structure of the quaternary ammonium surfactant headgroup.Increasing the size of this headgroup leads to an increase in rate of hydrolysis of the L ester and hence to an increase in enantioselectivity.This effect is attributed to a change in the degree of ion-pair formation with a carboxylate group that is present in the peptides.Compared to previous studies the results indicate that a chiral surfactant is not required for obtaining high enantioselectivities.
Micellar Enhancements of Rates of SN2 Reactions of Halide Ions. The Effect of Headgroup Size
Bacaloglu, Radu,Bunton, Clifford A.,Ortega, Francisco
, p. 1497 - 1502 (2007/10/02)
Observed first-order rate constants for reaction of methyl naphthalene-2-sulfonate with Cl- or Br- in micelles of cetyltrialkylammonium halide (C16H33NR3X, R = Me,Et,n-Pr,n-Bu, X=Cl,Br) increase monotonically with increasing surfactant and halide ion concentrations and tend to limiting values.The variation of rate constants with concentrations of surfactant and halide ions can be fitted to an equation that accounts for the distribution of both reactants between water and micelles.Fractional micellar ionization, α, increases, i.e., the affinity of the micelles for the halide ion decreases, with increasing bulk of the N-alkyl groups, but the second-order rate constants at the micellar surface and the overall rate constants increase.The rate effects of the micelles of the bromide ion surfactants can be understood in terms of NMR evidence on the micellar binding of the reactants and their location at the micellar surface.The reactivity increase with increasing headgroup bulk is related to the disruption of the hydration of Br- and to the electrostatic interaction of the naphthalene ?-system with cationic nitrogen.
PHOSPHORORGANISCHE VERBINDUNGEN 95. Beschleunigte Hydrolyse von Organophosphorverbindungen durch Phasentransferkatalyse und H2O2 als Supernucleophil
Horner, Leopold,Kappa, H. Wilfried
, p. 339 - 348 (2007/10/02)
The alkaline hydrolyses of the physiologically active phosphor compounds: butyl-phenylfluorophosphonate 1 and di-isopropyl-fluorophosphate were studied under phase-transfer (PT) conditions.The influence of pH, the structure of the phase-transfer catalyst, the nature of the organic phase and the use of the supernucleophile HO2- on the hydrolysis was investigated.The hydrolysis of 1 is accelerated by a factor of ca. 550 (toluene) resp. ca. 520 (tetrachloroethylene) compared with the uncatalysed reaction.In concrete terms, the compound 1 can be completely hydrolysed in three (tuloene) resp. in one minute (tetrachloroethylene) under optimal conditions.