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  • 2020-2022
  • 1970-1974  (3)
  • 1960-1964  (5)
  • 1890-1899
  • Alkenes
  • 1
    Digitale Medien
    Digitale Medien
    The syn and anti Steric Course in Bimolecular Olefin-Forming Eliminations (1972)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 200-214 
    Details
    ISSN: 0570-0833
    Schlagwort(e): Elimination ; Stereochemistry ; Alkenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Earlier evidence led to the view that in bimolecular olefin-forming eliminations the anti steric course is generally preferred over the syn. Recent experiments, however, show that in some common bimolecular elimination reactions, notably those involving onium bases, syn- and anti-eliminations proceed side by side, the former preferentially leading to the trans- and the latter to the cis-olefins.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/anie.197202001
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  • 2
    Digitale Medien
    Digitale Medien
    Metal-Olefin and -Acetylene Bonding in Complexes (1972)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 596-606 
    Details
    ISSN: 0570-0833
    Schlagwort(e): Bond theory ; Alkenes ; Alkynes ; Alkene ligands ; Alkyne ligands ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The molecular orbital (MO) and valence bond (VB) descriptions of the bonding in metalolefin and -acetylene complexes are examined in relation to their ability to explain the known properties of these complexes. It is concluded that whereas there are difficulties with the valence bond description, the molecular orbital description can satisfactorily explain all the known properties of these complexes and has the necessary versatility to enable it to be readily applied to any series of metal-olefin or -acetylene complexes. It is further shown that olefin and acetylene complexes can be usefully divided into two main classes: those that resemble the platinum(II)-complexes (class S), and are either square-planar or octahedral with essentially free rotation about the metal-olefin bond; and those that resemble platinum(0)-complexes (class T) and are either trigonal planar or trigonal bipyramidal and in which there is no rotation about the metal-olefin or -acetylene bond.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/anie.197205961
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  • 3
    Digitale Medien
    Digitale Medien
    Reactions of Electron-Rich Olefins with Proton-Active CompoundsDedicated to Professor Otto Bayer on the occasion of his 70th birthday (1972)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 964-973 
    Details
    ISSN: 0570-0833
    Schlagwort(e): Proton-active compounds ; Electron-rich alkenes ; Alkenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Proton-active substances react with certain electron-rich olefins with cleavage of the central C=C double bond to give compounds that can be formally regarded as insertion products of nucleophilic carbenes. If they satisfy certain structural conditions, they isomerize with β elimination to give open-chain compounds. Both CH-acidic compounds and compounds containing NH or OH groups can undergo this reaction. The mechanisms are discussed, and the importance of the intermediate products to biochemistry (thiamine, tetrahydrofolic acid) is indicated.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/anie.197209641
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  • 4
    Digitale Medien
    Digitale Medien
    Polar Addition of Hydrogen Halides onto OlefinsThis work was supported by a grant from the National Science Foundation. (1964)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 3 (1964), S. 245-249 
    Details
    ISSN: 0570-0833
    Schlagwort(e): Addition ; Alkenes ; Electrophilic reactions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Various structures have been proposed for the intermediates of electrophilic additions onto olefins; these include halonium ions, classical carbonium ions, π-complexes (i.e. nonclassical carbonium ions), and π-complexes with back-coordination. It is shown here that it is impossible to use any one of these entities alone to explain all such electrophilic additions; the electrophile itself determines the nature of the transition state formed. Polar addition of hydrogen halides onto olefins appears to proceed via a classical carbonium ion which does not occur as the free ion but as an undissociated ion pair. Various other mechanisms have been excluded by studies reported here of the stereochemical course of such additions.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/anie.196402451
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  • 5
    Digitale Medien
    Digitale Medien
    Type and Extent of Isomerization of Straight-Chain Mono-olefins during the Koch Carboxylic Acid SynthesisReported in part at the meeting of the Gesellschaft Deutscher Chemiker, Aachen 1961; Angew. Chem. 73, 767 (1961). (1963)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 719-722 
    Details
    ISSN: 0570-0833
    Schlagwort(e): Koch carboxylic acid synthesis ; Carboxylic acids ; Alkenes ; Isomerization ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: When straight-chain mono-olefins, from pentene to decene, are subjected to the Koch carboxylic acid synthesis by the addition of CO and H2O or CH3OH in the presence of strongly acidic catalysts, not only the expected secondary acids, but also mixtures of a specific type of tertiary acids or their methyl esters are formed. When the catalysts contain boron trifluoride, the secondary acids are formed in ratios of isomers which are, within the scope of this investigation, independent of the experimental conditions and which agree well with the values calculated from the isomer equilibria of the corresponding n-olefins. Using concentrated sulfuric acid as catalyst, a larger proportion of tertiary acids is obtained than with BF3-catalysis, and amongst the secondary acids, those isomers predominate in which the COOH group is situated near the centre of the molecule.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/anie.196307191
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  • 6
    Digitale Medien
    Digitale Medien
    Emulsion Polymerization of Vinyl Monomers under the Influence of Ionizing Radiation (1963)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 295-308 
    Details
    ISSN: 0570-0833
    Schlagwort(e): Emulsion polymerization ; Polymerization ; Polymerization ; Alkenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ionizing radiation induces the polymerization of some vinyl monomers in aqueous emulsion with high radiation yields. With identical emulsion compositions, the kinetics of this reaction and the kinetics of emulsion polymerization induced by water-soluble initiators are very similar. The rate of reaction in emulsion polymerization is about one hundred times greater than in bulk polymerization. The initiation of emulsion polymerization by means of ionizing radiation permits uniform “illumination” of the reacting volume, as well as almost any desired variation in the frequency of initiation during the reaction. The sharp decrease in the overall rate of reaction when initiation is interrupted during emulsion polymerization of styrene induced by γ-rays contradicts the earlier concept of sharply separated reaction zones.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/anie.196302951
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  • 7
    Digitale Medien
    Digitale Medien
    Reactions of Olefins with the Titanium-Carbon BondDedicated to Prof. Dr. Karl Ziegler on the occasion of his 65th birthday (1963)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 704-714 
    Details
    ISSN: 0570-0833
    Schlagwort(e): Titanium ; Alkenes ; Polymerization ; Titanium ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: At low temperatures, ethylene and α-olefins (Δ1-olefins or 1-alkenes) are rapidly converted into oligomrs by the two-component organometallic catalyst CH3TiCl3·CH3AlCl2. To achieve smooth oligomerizations, aromatic or chlorinated hydrocarbons must be used as solvents. Although the activity of the titanium-carbon bond is enhanced by the aluminum component of the catalyst, the aluminum and its methyl group do not participate in the reaction proper; the latter proceeds exclusively at the titanium-carbon bond. The reaction will olefins can be used as an analytical method for the quantitative determination of the titanium-carbon bond in admixture with the organoaluminum component. It is thus possible to follow the reaction leading to formation of the catalyst from titanium tertrachloride, as well as the processes occurring at the titanium-carbon bond during the oligomerization of olefins. All the observations indicate that the catalyst possesses an ionic structure which is determined by the solvent. It is shown that the initial reaction step probably involves formation of a complex between the olefin and the alkyltitanium cation. The reaction scheme proposed is based on organometallic reactions which are characterized by carbanion and hydride transfers within the olefin-cation complex. This mechanism, which is unusual for Ziegler catalysts, is due to the predominance of hydride transfers.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/anie.196307041
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  • 8
    Digitale Medien
    Digitale Medien
    The Oxidation of Olefins with Palladium Chloride Catalysts (1962)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 1 (1962), S. 80-88 
    Details
    ISSN: 0570-0833
    Schlagwort(e): Oxidation ; Palladium ; Catalysis ; Alkenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The oxidation of olefins to carbonyl compounds with palladium compounds, especially the oxidation of ethylene to acetaldehyde, is at present carried out on a technical scale. The reaction takes place via a palladium-olefin complex, the formation of which is inhibited by halide ions. Hydrolysis to the carbonyl compound is inhibited by hydrogen ions. The knowledge gained by studying the reaction of olefins with pure solutions of palladium salts allows important conclusions to be drawn concerning the action of technical catalyst solutions containing copper and palladium chloride.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/anie.196200801
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