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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 859-873 
    ISSN: 0009-2940
    Keywords: Benzoquinones, substituted ; Cyclic voltammetry ; Cathodic dioxygen reduction, mediated ; Anodic Wacker oxidation, mediated ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydroxy- (1a-3a) and hydroxyalkyl-substituted benzoquinones (6a-8a, 27a), suited to be immobilized by esterification with polyacrylic acid, are prepared. Their cathodic reduction potential Ep,c (1) correlates linearly with their substituent constant. The cathodic reduction of dioxygen and the palladium(II)-catalyzed anodic oxidation of alkenes are mediated by the benzoquinones 7b, 8b and 27b, respectively.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1399-1414 
    ISSN: 0887-624X
    Keywords: plasma polymers ; oxidation ; XPS ; FTIR ; SEM ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Long-term compositional changes were observed when n-hexane plasma polymers were stored in air at ambient temperature. These post-deposition changes were monitored over periods exceeding one year using XPS, grazing angle FTIR, and SEM. A rapid initial increase in the oxygen content was followed by a slower oxygen uptake, which continued for many months. In contrast to the reported autocatalytic acceleration of the oxidation of polyolefins, the rate of oxidation of n-hexane plasma polymers was found to decrease continuously, and it did not proceed to the same extent toward higher oxidation states. The plasma polymer coatings did not show physical manifestations of oxidative degradation such as cracking, reduction in thickness, or loss of physical integrity. Comparison of the XPS and FTIR data suggested that the top few nanometers of the plasma polymer coatings oxidized at a faster rate than the “bulk.” The experimental data were interpreted using a model comprising reactions known from the oxidative degradation of polyolefins: carbon-centered radicals, trapped in the course of the plasma deposition, combine with atmospheric oxygen to form metastable peroxy radicals and hydroperoxides, which decompose to generate a variety of stable product groups such as hydroxyl, carbonyl, and carboxylic groups. There was broad agreement between the XPS data and the time dependence of particular species in model calculations. © 1994 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 29 (1994), S. 153-154 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 4
    ISSN: 0170-2041
    Keywords: Kolbe electrolysis ; Radical cyclization ; Electrochemical dehalogenation ; Prostaglandins ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The key intermediate of a novel synthesis of prostaglandin precursors, (1′R,4′S,3R/S)-3-(cis-4-acetoxycyclopent-2-enyl oxy)-3-ethoxypropionic acid (3), is prepared by two different synthetic sequences: In a first strategy transacetalization of ethyl 3,3-diethoxypropionate (6) with (1R, 4S)-4-acetoxy-1-hydroxy-2-cyclopentene (7) leads to the formation of the mixed acetal 8. By subsequent hydrolysis and acylation 8 could be converted into acid 3 in six steps in 6% overall yield. However, the generation of acid 3 by bromoalkoxidation of 3-ethoxyacrylates 13d, e and subsequent electrochemical reduction proved to be more efficient. In this reduction it is possible to debrominate the α-bromo esters 14d, e and to remove the 2-haloethyl ester group in one step. Using this reaction sequence, we could synthesize acid 3 in five steps in 38% overall yield.
    Additional Material: 3 Tab.
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  • 5
    ISSN: 0170-2041
    Keywords: Kolbe electrolysis ; Radical cyclization ; Si-C bond oxidation ; Prostaglandins ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The α-silyl-substituted carboxylic acids 4 and 10 were prepared and with other coacids subjected to a mixed Kolbe electrolysis with β-cyclopentenyloxypropanoate 1. The stereochemical course of this cyclization reaction was determined on the basis of the 4-methyl-substituted product 23 by 1H-NMR-NOE spectroscopy. Conversion of the bicyclic reaction products 21b-d to advanced prostaglandin precursors such as lactone 30 was achieved in few steps.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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