A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.
127I NMR studies, as well as quadrupole splitting experiments performed by 2H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.
The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles. 相似文献
Some nickel, copper, and silver salts or complexes are efficient catalysts for the oxidation of benzylic ethers with oxygen in 1,2-dimethoxyethane. Salts of the weakly coordinating anion trifluoroacetate are particularly efficient, approaching (and, in some cases, improving) the yields obtained with cobalt(II) chloride, the best catalyst so far reported. 相似文献
Lévy processes in matrix Lie groups are studied. Subordination (random time change) is used to show that quasi-invariance of the Brownian motion in a Lie group induces absolute continuity of the laws of the corresponding pure jump processes. These results are applied to several examples which are discussed in detail. 相似文献
Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of 1H and 13C NMR spectroscopy and DNOE experiments. 相似文献
In this Note, we give a necessary and sufficient condition for Lagrangians in a symplectic vector bundle to be deformed stably into transversal Lagrangians. In the case of three Lagrangians, we show that the associated Grothendieck group can be identified with a Hermitian K-theory group. To cite this article: M. Karoubi, M.L. Lapa de Souza, C. R. Acad. Sci. Paris, Ser. I 342 (2006).相似文献