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201.
Nonmetal oxidation catalysts have gained much attention in recent years. The reason for this surge in activity is 2-fold: On one hand, a number of such catalysts has become readily accessible; on the other hand, such catalysts are quite resistant toward self-oxidation and compatible under aerobic and aqueous reaction conditions. In this review, we have focused on five nonmetal catalytic systems which have attained prominence in the oxidation field in view of their efficacy and their potential for future development; stoichiometric cases have been mentioned to provide overview and scope. Such nonmetal oxidation catalysts include the alpha-halo carbonyl compounds 1, ketones 2, imines 3, iminium salts 4, and nitroxyl radicals 5. In combination with a suitable oxygen source (H2O2, KHSO5, NaOCl), these catalysts serve as precursors to the corresponding oxidants, namely, the perhydrates I, dioxiranes II, oxaziridines III, oxaziridinium ions IV, and finally oxoammonium ions V. A few of the salient features about these nonmetal, catalytic systems shall be reiterated in this summary. The first class entails the alpha-halo ketones, which catalyze the oxidation of a variety of organic substrates [figure: see text] by hydrogen peroxide as the oxygen source. The perhydrates I, formed in situ by the addition of hydrogen peroxide to the alpha-halo ketones, are quite strong electrophilic oxidants and expectedly transfer an oxygen atom to diverse nucleophilic acceptors. Thus, alpha-halo ketones have been successfully employed for catalytic epoxidation, heteroatom (S, N) oxidation, and arene oxidation. Although high diastereoselectivities have been achieved by these nonmetal catalysts, no enantioselective epoxidation and sulfoxidation have so far been reported. Consequently, it is anticipated that catalytic oxidations by perhydrates hold promise for further development, especially, and should ways be found to transfer the oxygen atom enantioselectively. The second class, namely, the dioxiranes, has been extensively used during the last two decades as a convenient oxidant in organic synthesis. These powerful and versatile oxidizing agents are readily available from the appropriate ketones by their treatment [figure: see text] with potassium monoperoxysulfate. The oxidations may be performed either under stoichiometric or catalytic conditions; the latter mode of operation is featured in this review. In this case, a variety of structurally diverse ketones have been shown to catalyze the dioxirane-mediated epoxidation of alkenes by monoperoxysulfate as the oxygen source. By employing chiral ketones, highly enantioselective (up to 99% ee) epoxidations have been developed, of which the sugar-based ketones are so far the most effective. Reports on catalytic oxidations by dioxiranes other than epoxidations are scarce; nevertheless, fructose-derived ketones have been successfully employed as catalysts for the enantioselective CH oxidation in vic diols to afford the corresponding optically active alpha-hydroxy ketones. To date, no catalytic asymmetric sulfoxidations by dioxiranes appear to have been documented in the literature, an area of catalytic dioxirane chemistry that merits attention. A third class is the imines; their reaction with hydrogen peroxide or monoperoxysulfate affords oxaziridines. These relatively weak electrophilic oxidants only manage to oxidize electron-rich substrates such as enolates, silyl enol ethers, sulfides, selenides, and amines; however, the epoxidation of alkenes has been achieved with activated oxaziridines produced from perfluorinated imines. Most of the oxidations by in-situ-generated oxaziridines have been performed stoichiometrically, with the exception of sulfoxidations. When chiral imines are used as catalysts, optically active sulfoxides are obtained in good ee values, a catalytic asymmetric oxidation by oxaziridines that merits further exploration. The fourth class is made up by the iminium ions, which with monoperoxysulfate lead to the corresponding oxaziridinium ions, structurally similar to the above oxaziridine oxidants except they possess a much more strongly electrophilic oxygen atom due to the positively charged ammonium functionality. Thus, oxaziridinium ions effectively execute besides sulfoxidation and amine oxidation the epoxidation of alkenes under catalytic conditions. As expected, chiral iminium salts catalyze asymmetric epoxidations; however, only moderate enantioselectivities have been obtained so far. Although asymmetric sulfoxidation has been achieved by using stoichiometric amounts of isolated optically active oxaziridinium salts, iminium-ion-catalyzed asymmetric sulf-oxidations have not been reported to date, which offers attractive opportunities for further work. The fifth and final class of nonmetal catalysts concerns the stable nitroxyl-radical derivatives such as TEMPO, which react with the common oxidizing agents (sodium hypochlorite, monoperoxysulfate, peracids) to generate oxoammonium ions. The latter are strong oxidants that chemoselectively and efficiently perform the CH oxidation in alcohols to produce carbonyl compounds rather than engage in the transfer of their oxygen atom to the substrate. Consequently, oxoammonium ions behave quite distinctly compared to the previous four classes of oxidants in that their catalytic activity entails formally a dehydrogenation, one of the few effective nonmetal-based catalytic transformations of alcohols to carbonyl products. Since less than 1 mol% of nitroxyl radical is required to catalyze the alcohol oxidation by the inexpensive sodium hypochlorite as primary oxidant under mild reaction conditions, this catalytic process holds much promise for future practical applications. 相似文献
202.
Christer Löfstedt Bill S. Hansson Erik Petersson Peter Valeur Andrew Richards 《Journal of chemical ecology》1994,20(1):153-170
Extracts of different body parts of adult Trichoptera were tested for electrophysiological activity. Extracts of the IVth and Vth abdominal sternites of femaleHydropsyche angustipennis, Rhyacophila nubila, andR. fasciata, containing a paired exocrine gland, elicited significant electroan-tennographic responses when tested on conspecific male antennae. The paired gland occurs also in males of all the species, and inH. angustipennis, extracts from males were more active than female extracts when tested on male antennae. Female and male extracts from all species were analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). EAD-active peaks in female extracts, stimulating male antennae, were identified inH. angustipennis as nonan-2-one; and inR. nubila andR. fasciata as heptan-2-one, heptan-2-ol, nonan-2-one, and nonan-2-ol. EAD-active components from maleH. angustipennis stimulating male antennae were octan-2-one, nonan-2-one (major peak), (Z)-6-nonen-2-one, decan-2-one, and a methylbranched decan-2-one. Female extracts and synthetic mixtures of compounds identified from femaleH. angustipennis andR. fasciata were tested for attractivity in the field. High catches with control traps obscured the results, but a synthetic mixture of the four identified compounds was significantly attractive and not different from female extracts for attracting maleR. fasciata. InH. angustipennis, a synthetic six-component male blend, in which nonan-2-one was the major component, attracted significant numbers of male and femaleH. angustipennis. Extracts of maleR. nubila andR. fasciata contained acetophenone and hexanoic and octanoic acids but did not have any electrophysiological or behavioral activity on either male or female antennae of conspecifics. The occurrence of a female sex pheromone inRhyacophila and an aggregation pheromone inHydropsyche corresponds to earlier described differences in mating behaviors in the Rhyacophilidae and Hydropsychidae. 相似文献
203.
N. Schönfeldt 《Journal of the American Oil Chemists' Society》1968,45(2):80-82
The course of the lime soap-dispersing action of various surfactants has been examined by use of a titrimetric method. Two
types of dispersants can be distinguished. With the addition of a surfactant of the first type, the concentration of the dispersed
fatty acid increases gradually. If a surfactant of the second type is used, a definite increase of the fatty acid concentration
first occurs after the addition of considerable amounts of the dispersant.
Ethylene oxide adducts and sodium triethylene glycol monolauryl ether sulfate behave like dispersants of the first type whereas
sodium dodecylbenzenesulphonate and sodium lauryl sulfate belong to those of the second type. The dispersing action of both
types of surfactants is discussed. 相似文献
204.
H. R. Spiegel J. Juilfs U. Neubert K. J. Euler J. W. Beck D. Besdo H. Winter H. Becker W. Neuberger R. Jung K. Herfort H. Bühler H. Göppl H. W. Hahnemann W. Siegel 《Forschung im Ingenieurwesen》1970,36(2):64-68
Ohne Zusammenfassung
VDI 相似文献
205.
Summary Morphology and thermal characteristics of poly (trimethylene terephthalate) (PTT)/ metallocene linear low-density polyethylene (m-LLDPE) blends with different amounts of a terpolymer based on glycidyl methacrylate (GMA), employed as a possible compatibilizer, were systematically examined. DMTA results show two distinct peaks for all neat blends associated with each phase. Melt crystallization degree of both phases in all the blends was observed to be reduced compared to pure components, except for that of PTT-rich phase in those blends with PTT as the matrix which slightly increases. Addition of the terpolymer to the system is found to effectively reduce the droplet size of the dispersed phase and increase phase adhesion. Also it increases the crystallinity of PTT in the system with PTT as the matrix. The influence of the compatibilizer is ascribed to the chemical interaction of PTT functional end groups with GMA functionalities. The efficiency of the terpolymer as a compatibilizer beyond 5 wt% content decreases which can be ascribed to the interface saturation and formation of micelles in the bulk phases. 相似文献
206.
M. Takeuchi S. Ueno E. Flöter K. Sato 《Journal of the American Oil Chemists' Society》2002,79(7):627-632
The binary phase behavior of SOS (1,3-distearoyl-2-oleoyl-sn-glycerol) and SLS (1,3-distearoyl-2-linoleoyl-sn-glycerol) was examined by using DSC and conventional and synchrotron radiation X-ray diffraction. The solid-solution phases
were observed in the metastable α and γ forms in all concentration ranges. Results indicated that the miscible γ form did
not transform to the β′ form when the mixtures were subjected to simple cooling from a high-temperature liquid to a low-temperature
solid phase. However, and α-melt-mediated transformation into β′ and β2 resulted in the formation of immiscible phases in concentration ranges of SLS below 30%. By contrast, at SLS concentration
ranges above 30%, the α-melt-mediated transformation caused crystallization of only the γ form, and β′ and β2 crystals did not appear. These results show that the specific interactions between SOS and SLS are operative in the phase
behavior of the mixture states of SOS and SLS. 相似文献
207.
Dorota Johansson Björn Bergenståhl 《Journal of the American Oil Chemists' Society》1992,69(8):728-733
The influence of water on the interactions between fat and sugar crystals dispersed in triglyceride (vegetable) oils was qualitatively
estimated from sedimentation and rheological experiments. The experiments were performed both with and without food emulsifiers
(monoglycerides and lecithins) present in the oil. The effects of minor natural oil components (nontriglycerides) on the interactions
and on emulsifier adsorption to the crystals were examined by comparing a commercial refined oil and a chromatographically
purified oil. The results show that water generally increases the adhesion between fat and sugar crystals in oils and also
increases the surface activity of the oil-soluble food emulsifiers. Minor oil components give a small increase in the adhesion
between fat and sugar crystals in oils, but do not influence the adsorption of food emulsifiers in any systematic way. 相似文献
208.
Peter Meszmer Karla Hiller Steffen Hartmann Alexey Shaporin Daniel May Raul David Rodriguez Jörg Arnold Gianina Schondelmaier Jan Mehner Dietrich R. T. Zahn Bernhard Wunderle 《Microsystem Technologies》2014,20(6):1041-1050
In this paper, a novel concept of a thermo-mechanical MEMS actuator using aluminum thin-film heaters on a thermal oxide for electrical insulation is presented. The actuator is part of an universal tensile testing platform for thermo-mechanical material characterization of one dimensional materials on a micro- and nano-scopic scale under different environmental conditions, as varying temperatures, pressure, moisture or even vacuum and is realised in BDRIE technology. It is shown, that the actuator concept fulfills the requirements for the use in a tensile loading stage along with heterogeneously integrated nanofunctional elements, following a specimen centered approach in line with bottom-up self-assembly processes. Simulation and experiment agree very well in the thermal and mechanical domain and allow subsequent optimisation of the actuator performance. 相似文献
209.
C. Flötgen M. Pawlak E. Pabo H. J. van de Wiel G. R. Hayes V. Dragoi 《Microsystem Technologies》2014,20(4-5):653-662
Wafer-level Cu–Sn intermetallic bonding is an interesting process for advanced applications in the area of MEMS and 3D interconnects. The existence of two intermetallic phases for Cu–Sn system makes the wafer bonding process challenging. The impact of process parameters on final bonding layer quality have been investigated for transient liquid phase wafer-level bonding based on the Cu–Sn system. Subjects of this investigation were bonding temperature profile, bonding time and contact pressure as well as the choice of metal deposition method and the ratio of deposited metal layer thicknesses. Typical failure modes in intermetallic compound growth for the mentioned process and design parameters have been identified and were subjected to qualitative and quantitative analysis. The possibilities to avoid abovementioned failures are indicated based on experimental results. 相似文献
210.
Maria Paola Bianchi Hans-Joachim Böckenhauer Juraj Hromkovič Lucia Keller 《Algorithmica》2014,70(1):92-111
In the online version of the well-known graph coloring problem, the vertices appear one after the other together with the edges to the already known vertices and have to be irrevocably colored immediately after their appearance. We consider this problem on bipartite, i.e., two-colorable graphs. We prove that at least ?1.13746?log2(n)?0.49887? colors are necessary for any deterministic online algorithm to be able to color any given bipartite graph on n vertices, thus improving on the previously known lower bound of ?log2 n?+1 for sufficiently large n. Recently, the advice complexity was introduced as a method for a fine-grained analysis of the hardness of online problems. We apply this method to the online coloring problem and prove (almost) tight linear upper and lower bounds on the advice complexity of coloring a bipartite graph online optimally or using 3 colors. Moreover, we prove that \(O(\sqrt{n})\) advice bits are sufficient for coloring any bipartite graph on n vertices with at most ?log2 n? colors. 相似文献