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PL
Przedstawiono doniesienia literaturowe dotyczące zastosowania cieczy jonowych jako efektywnych rozpuszczalników i katalizatorów w procesach utleniania ketonów do odpowiednich laktonów lub estrów. Przedstawiono kilka nowych rozwiązań dla reakcji Baeyera i Villigera (BV) z zastosowaniem wielu różnych utleniaczy, takich jak tlen, nadtlenek wodoru, kwas m-chloronadbenzoesowy, mononadtlenosiarczan potasu oraz nadtlenek bis(trimetylosililowy). Dodatkowo przedstawiono istotne zagadnienia związane z usprawnieniem aspektów technicznych, takich jak możliwość odzysku cieczy jonowej i jej ponownego użycia w reakcji, metody wydzielania produktów z mieszaniny poreakcyjnej czy możliwość prowadzenia procesu w układzie dwufazowym z wykorzystaniem stałego katalizatora.
EN
A review, with 38 refs., of several new methods for Baeyer-Villiger reaction with various oxidants (O2, H2O2, m-chloroperbenzoic acid, K peroxymonosulfate and bis(trimethylsilyl)  peroxide) in ionic liq. as solvents and oxidn. catalysts. Tech.  aspects of recycling of ionic liqs., product sepn. from postreaction mixt. and use of 2 – phase reaction systems with  solid catalyst were taken into consideration.
EN
This work presents the results of oxygen solubility in ionic liquids based on 1-alkyl-3-methylimidazolium cations. Solubility measurements have been carried out in gasometric apparatus at 22, 50 and 90graduate C under atmospheric pressure. We report the Henry's constants. In general the occurrence of carbon-fluorine bonds and carbon-hydrogen bonds in ionic liquids (ILs) which can create hydrogen bonds with dissolved oxygen, significantly affects the growth of value of solubility constant KH. Additionally, the stability of ILs towards molecular oxygen was tested. All ILs used in this study were stable in the presence of oxygen and free-radical initiator.
5
Content available remote Synthesis of peroxyesters using polymer-supported phase transfer catalysts
EN
A synthesis method of peroxyesters from alkyl hydroperoxides and acid chlorides catalyzed by polymer-supported phase transfer catalysts was introduced. This method makes it possible for the catalyst to be easily separated from the reaction product and be used in the continuous process.
7
Content available remote Synteza nadtlenoestrów organicznych w środowisku cieczy jonowych
PL
W niniejszej pracy opracowano nową efektywną syntezę nadtlenoestrów organicznych w wyniku reakcji aclylowania wodoronadtlenków alkilowych wobec 30% roztworu wodnego NaOH lub pirydyny w środowisku wybranych cieczy jonowych.
EN
A new convenient and effective method of synthesis of organic peroxyesters has been developed, which involves acylation of hydroperoxides in the presence of NaOH (30% water solution) or pyridyne in room temperature ionic liquids as a novel media.
EN
The synthesis of mixed organic peroxides by reaction of alkyl halides with tertiary hydroperoxides under basic phase-transfer catalysis conditions was described.
EN
The paper shows the results of the study on application of aqueous Na2CO3 solution for the reaction of alkyl hydroperoxides with acid chlorides in the presence of phase transfer (PT) catalysts. Observed reaction rate constants were determined. The effect of stirring speed, Na2CO3 amount, acid chloride structure and PT catalyst on the process run was investigated. The method has been proven to be effective, rendering high yields of peroxyesters (60-94%) under relatively mild conditions.
EN
Organic peroxides are an interesting group of organic compounds. The O-O bonds in their structure warrant their properties determining the range of their application. The chemistry of peroxy substances is a branch of knowledge which is continuously developing. In the course of recent years much progress has been achieved both in the field of synthesizing new peroxides systems and in applaying them, particularly concerning their biological transformations. A peroxide bond displays a low dissociation energy (20-50 kcal/mol) and that is why they are rather unstable. The reactions of peroxy substances may be divided into homolytic (radical) and heterolytic (ionic) ones. The most popular reaction of the monomolecular homolytic decomposition of the peroxide bond into radicals, occuring under the influence of temperature or radiation, is typical for all classes of peroxy substances and has found practical application. Theretically possible is also a molecular heterolytic decomposition of the peroxide bond into ions. Such a decomposition cannot compete, however, with the homolitic one and is required only in few specific cases. The O-O bond can also undergo transfomations in result of reactions with other substances. Also these reactions may be divided into two fundamental types. Some peroxy substances, e.g. hydroperoxides and peroxy acids, are electron donors and may occur in the reactions as nucleophiles. On the other hand, peroxy substances display the properties of "soft electrophiles" reacting with nucleophilic reagents. The result of such a reaction is a heterolytic decomposition of the peroxide bond. This ambivalent feature of peroxy substances becomes most visible in the natural process of peroxy acids in a basic medium, in which the RCO3- ion plays the role of a nucleophile attacking the non ionized particle (the electrophile). In recent years it has been more and more often stipulated that the reactions of peroxides with nucleophiles run in compliance with the mechanism of the electron transfer (SET) from the nucleophile particle to the oxygen atom of the peroxy bond, in the result of which radicals and radical ions are formed in the course of this reaction. It ought to be stressed that it is extremely difficult to determine the mechanisms of many reactions of peroxy substances explicitly, becouse these types of reactions (SN2, SET) may take place simultaneously and in most cases lesd to the formation of some products.
12
EN
The first-order decomposition rates of asymmetric cumyl propyl peroxide (CPP) in various solvents have been investigated. The differences in rates are discussed in terms of the polar character of reaction transition state. The ratio of reaction products derived from cumyloxyl radical PhC(Me)2O* (1-phenyl-l-ethanon to 2-phenylpropan-2-ol) varies significantly with solvents used.
EN
The acylation of alkyl hydroperoxydes with acid chlorides under the phase transfer conditions (PTC) is studied. An evident catalytic effect was observed. This reaction can be considered as a convenient method for the synthesis of organic peresters.
PL
W ostatnich latach problemy ochrony środowiska odgrywają kluczową rolę przy projektowaniu technologii wielkotonażowych. Mniejszą uwagę zwraca się na te zagadnienia w przypadku małych produkcji zapominając, że właśnie w tych przypadkach stosunek substancji odpadowych do pożądanego produktu jest niejednokrotnie większy niż w produkcjach masowych. Dodatkowe problemy wynikają również z różnorodności odpadów. Duże możliwości poprawy w tym zakresie daje kataliza przeniesienia międzyfazowego (PTC). Jest to nowoczesna technika coraz częściej stosowana we współczesnej przemysłowej syntezie organicznej. Pozwala ona na: - zmniejszenie ilości uciążliwych odpadów, - przeprowadzenie procesu w znacznie łagodniejszych warunkach niż w przypadku reakcji prowadzonych bez udziału katalizatora, a więc łatwiejszą kontrole procesu, - zwiększenie szybkości reakcji, co wiąże się zmniejszeniem kosztów inwestycyjnych, - zmniejszenie kosztów materiałowych (wyeliminowanie drogich rozpuszczalników, podwyższenie wydajności reakcji), - łatwe wydzielanie produktów oraz większe bezpieczeństwo pracy.
EN
The present work deals with the synthesis method of peroxides from sodium and potassium organic peroxides and alkil or acyl halides a two-phase solid/organic solvent system by phase transfer catalysis. The effect of various parameters including temperature, structure of the reagents, catalysts and reaction conditions on the progress of the reaction are discussed. The yield of this process is in range 60-90 %. PTC technique makes this process very selectivity and minimizes amounts of wastes. The mechanism of investigated process has been examined. When the tetrabutylammonium salts was used as a catalyst the tetra-butylammonium alkyl peroxide has bee found as by products. The reaction of tetraalkylammonium alkylperoxides with alkyl halides has been reported. Mixed dialkyl peroxides and peroxyesters has been found as products of these reaction. A method has been developed for the analysis of several important dialkyl peroxides.
EN
Reactivity of organic peroxy compounds, specially dialkyl peroxides is described. The knowlodge of chemical properties and reactivity of these substances is essential for the understanding of many practical aspects, e.g. the processes of ageing and explosion, waste management and biochemical processes. Peroxides reactions have been systematized using monomolecular and bimoleculr fragmentation. Among monomolecular reactions are homolytic and heterolytic decomposition; among bimolecular ionic and radical reactions.
EN
The homogeneous decomposition of various asymmetric dialkyl peroxides ROOR' (R=C6H5(CH3)2; R'=Et, Pr, Bu, Bu(i), Bu(s), Bu(t), n-heptyl, n-dodecyl and allyl) is examined by the measurement of autooxidation of isopropylbenzene in the presence of peroxides as initiators. Rate constants and activation parameters are determined and the size effect and type of alkyl group R' on stability of O-O bond is discussed.
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