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
To find an effective extraction and removal method for palladium(II), which is one of the main fission products from an acidic nuclear spent fuel solution, the extraction behavior of palladium(II) from a nitric acid medium by an acidic chelating extractant, 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5-one (HPMTP) and a tertiary amine of high molecular weight, tri-n-octylamine (TOA), has been studied by spectrophotometry. A noticeable antagonistic extraction effect was observed in the extraction system under the given conditions. To understand this phenomenon, a preliminary investigation was performed to explain the mechanism of this reaction. According to the theory of corresponding solutions (TCS), the association reaction between HPMTP and TOA is proposed in the organic phase. An associated species, HPMTP·TOA, formed through hydrogen bonding in a chloroform medium might be the main reason why an antagonistic extraction effect occurred. The association constant between HPMTP and TOA was calculated to be 2.86±0.05. 相似文献
The results of studies on electrosynthesis involving carb- and heteroanions generated by cathodic deprotonation of acids (CDA), carried out in the laboratory headed by the author, are surveyed. These studies resulted in the elaboration of efficient electrochemical versions of the known Michaelis-Becker, Wittig-Horner, and Perkin reactions; electrochemical analogs of homolytic aromatic substitution, alkylation, heterocyclization,etc. were developed. Based on CDA, convenient and promising methods for preparing variousN-, O-, P-, S-, andC-alkylated and arylated substances have been developed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1411–1422, August, 1995.The author is grateful to Professor V. A. Dorokhov, Professor V. P. Litvinov, and researchers from the laboratories of N. D. Zelinsky Institute of Organic Chemistry headed by them, who participated in joint studies.The work was carried out with financial support from the International Science Foundation (Grant No. MHYOO). 相似文献
The fluorescence dynamics parameters of the fluorescent transient flavin-luciferase species from the typesVibrio fischeri andPhotobacterium leiognathi are presented. The fluorescence anisotropy decay is a single exponential function for both types. The correlation time is 70 ns for theP. leiognathi fluorescent transient intermediate (2°C, aqueous buffer, pH 7.0), consistent with the rotational correlation time of the luciferase macromolecule (77 kD) to which the flavin fluorophore is rigidly attached. In contrast, for theV. fischeri species the observed correlation time for the anisotropy decay function is 133 ns. This suggests that protein self-association occurs in theV. fischeri case and this is confirmed by filtration, where the fluorescent transient fromV. fischeri does not pass through a 100,000 molecular weight cutoff membrane, whereas theP. leiognathi species does. The filtration method also demonstrates self-association in the luciferase peroxyflavin and photoflavin fromV. fischeri. A monomer-dimer equilibrium also explains the previously reported high correlation times for theV. harveyi luciferase-flavin species. It is proposed that the self-association competes with the lumazine protein interaction in the bioluminescence reaction. 相似文献
The wreath product of finite association schemes is a natural generalization of the notion of the wreath product of finite permutation groups. We determine all irreducible representations (the Jacobson radical) of a wreath product of two finite association schemes over an algebraically closed field in terms of the irreducible representations (Jacobson radicals) of the two factors involved. 相似文献
The association constant K of mono-acetato complex of Tb3+ has been determined at normal p and T conditions by measurement of its luminescence lifetime in aqueous solution containing increasing concentrations of acetate. Two experimental arrangements used for the measurement are described. 相似文献
Using flow microcalorimetry, the ion association reaction M2+(aq)+Fe(CN)
64–
(aq)=MFe(CN)
62–
(aq) (M=Ca, Mg) has been studied at 25°C over the ionic strength range 0.02 to 0.08 mol-dm–3. Analyses of the data to obtain Ho, the enthalpy change at infinite dilution, are described. The value obtained for Ho is sensitive to the kind of functions used to correct for non-ideal behavior. 相似文献