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
1. INTRODUCTION Methionine, namely 2-amido-4-thiomethyl butyric acid with a structure of CH3SCH2CH2CHCOOH, is one of the essential amino acids and has two natural enantionmers, D and L-methionine. The mixture of L- and D-isomers can be used as analeptics or nutritive additives to maintain the equilibrium of amino acids of feed [1,2]. L-methionine can release active methyl and accelerate the synthesis of choline, which further speeds up the conversion of the lipid accumulated in liv… 相似文献
1. INTRODUCTION The development of efficient polymer-supported catalysts has attracted much attention [1]. For obtaining polymeric catalysts, catalytically active groups were introduced onto polymers mostly by copolymerization of the appropriate monomers bearing the desired catalyticfunctionalities (e.g. imidazole, OH, and COOH) or by modification of preformed polymers.Another possibility involves the attachment of side chains, containing the desired arrangement of functional groups, o… 相似文献
5,6-Dihydro-OSW-1 (1) was synthesized following our previous procedure for the total synthesis of OSW-1. This compound demonstrated slightly stronger potency than that of OSW-1 against the growth of cancer cells. 相似文献
Six new 13-O-acylavermectin Bl aglycones(3-8) were synthesized from avermectin B1 aglycone and their bioactivities were evaluated against Spodoptera exigua, Spodoptera eridania, Tetranychus urticae and Aphis fabae. 相似文献
A sensitive analytical method to identify active metabolites of bitespiramycin in rat urine and bile was developed by liquid chromatography-electrospray ionization tandem mass spectrometry(LC/ESI-MS^n).Bitespiramycin and its major active metabolites in rat urine and bile were isolated and identified as M1 serial(spiramycin Ⅰ,Ⅱ,Ⅲ),M2 serial(platenomycin A1,josamycin and leucomycin A1) and M3 serial(deisovalerylplatenomycin A1,deisovaleryljosamycin,deisovalerylleucomycin A1). 相似文献
The relation of the isoelectric point (IEP) and the point of zero net charge (PZNC) of the hydrotalcite-like compounds was discussed. It was found that the IEP does not equal to the PZNC and the IEP is higher than the PZNC. The structural positive charges existing in the HTlc,which cause the difference between the IEP and the PZNC. The effects of the structural positive charges of the HTlc on its IEP and PZNC are the same as the specific adsorption of metal cations. 相似文献
By extracting combinatorial structures in well-solved nonlinear combinatorial optimization problems, Murota (1996,1998) introduced the concepts of M-convexity and L-convexity to functions defined over the integer lattice. Recently, Murota–Shioura (2000, 2001) extended these concepts to polyhedral convex functions and quadratic functions in continuous variables. In this paper, we consider a further extension to more general convex functions defined over the real space, and provide a proof for the conjugacy relationship between general M-convex and L-convex functions.Mathematics Subject Classification (1991): 90C10, 90C25, 90C27, 90C35This work is supported by Grant-in-Aid of the Ministry of Education, Culture, Sports, Science and Technology of Japan 相似文献
The notion of Kuratowski convergence is applied to describe a kind of convergence in the context of holomorphic functions. We associate it to a convenient topology, explore its relation with the compact-open topology, thus providing a new set theoretic point of view of this classic topology, and present it in the framework of set-valued mappings. 相似文献