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  • Inorganic Chemistry  (2)
  • Industrial Chemistry and Chemical Engineering  (1)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1679-1682 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Anodic Oxidation of Cycloaliphatic Mono- and Diethers in Aqueous ElectrolytesThe anodic oxidation of cycloaliphatic ethers such as tetrahydrofuran5) and tetrahydro-2H-pyran (1) as well as cycloaliphatic diethers such as 1,4-dioxane (3) and 1,3-dioxolane (6) was investigated under various conditions in aqueous 1 M H2SO4. The primary products in all cases are those of anodic hydroxylation in the 2-position to yield cyclic hemiacetals. This oxidation gives with platinum current efficiencies which are much larger than the results of the anodic methoxylation in methanol. The high selectivity in some cases is explained in terms of an O-insertion from PtO2. - The follow-up oxidation leads in the case of the cyclic monoethers to lactones, predominantly with lead dioxide. δ-Valerolactone is synthesized with more than 60% current efficiency from 1. With diethers 3 and 6, anodic products of ring fragmentation are formed. The product distribution is indicative of an O-insertion under ring expansion.
    Notes: Die anodische Oxidation cycloaliphatischer Ether wie Tetrahydrofuran5) und Tetrahydro-2H-pyran (1) sowie cycloaliphatischer Diether wie 1,4-Dioxan (3) und 1,3-Dioxolan (6) wurde unter verschiedenen Elektrolysebedingungen in wäßriger 1 M H2SO4 untersucht. Übereinstimmend wird primär durch anodische Hydroxylierung in 2-Stellung ein cyclisches Halbacetal gebildet. An Platin sind die Stromausbeuten viel höher als bei der analogen Methoxylierung in Methanol. Die teilweise erreichte hohe Selektivität wird auf eine spezifische O-Insertion aus PtO2 zurückgeführt. - Die Weiteroxidation führt bei den cyclischen Monoethern, vor allem an Bleidioxid, zum Lacton. Aus 1 entsteht mit über 60% Stromausbeute das δ-Valerolacton. Im Fall der Diether 3 und 6 bilden sich Produkte der anodischen Ringfragmentierung; das Produktspektrum ist indikativ für eine O-Insertion unter Ringerweiterung.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 3771-3780 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Anodic Oxidation of 2-Cyanoethanol to Cyanoacetic Acid2-Cyanoethanol (3-hydroxypropiononitrile, 1) has been oxidized electrochemically in aqueous sulfuric acid at platinum- and lead dioxide anodes with current densities of 30 - 200 mA cm-2 to give cyanoacetic acid (3). Current efficiencies and material yields were up to 60%. Side products are HCN via an anodic attack at β-CH2 with 8 - 15% and cyanoacetaldehyde with 3 - 13% current efficiency on platinum. In principle, HCN can be recycled to new starting material and cyanoacetaldehyde to yield further product. Electrooxidation at Pt takes place at an anode, which is partially covered with platinum oxides. High over-voltages are interpreted in terms of voltage drop in a rigid organic adsorbate layer.
    Notes: 2-Cyanethanol (3-Hydroxypropionitril, 1) wird in schwefelsauren, wäßrigen Elektrolyten an Platin- oder Bleidioxid-Anoden bei Stromdichten von 30 - 200 mA/cm2 elektrochemisch zu Cyanessigsäure (3) oxidiert. Die Strom- und Materialausbeuten erreichen 60%. Als Nebenprodukte entstehen HCN über einen anodischen Angriff am β-CH2 mit 8 - 15% und Cyanacetaldehyd mit 3 - 13% Stromausbeute an Platin. Im Prinzip kann HCN in neues Edukt und Cyanacetaldehyd in das Produkt übergeführt werden. Die Elektrooxidation an Platin findet an teilweise mit Platinoxiden bedeckten Anoden statt. Die hohen Überspannungen werden als Spannungsabfall in einer starren, organischen Adsorbatschicht gedeutet.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Manganese mixed oxide composite layers of about 1 μm thickness on titanium sheet as substrate were fabricated by firing of the corresponding nitrates at a typical temperature of 400°C in air. The activity of these anodes was evaluated by cyclic voltammetry (10 mV/s) and the stability was determined by chronopotentiometry (2.5 mA/cm2) in 1M H2SO4. The oxidation of 2-propanol was examined as a simple electroorganic model reaction. The quality of a first category of mixed oxides with general composition MnMe2O4 decresed in the order Me = Co, Ni, Fe. In a second group with the general formula MeMn2O4 a decrease in the order Me = Co, Cu, Fe, Ni, Ti, Zn, Cd, Ca, Mg, (Zn, Ge), Li was observed. The corresponding candidates of the second group were superior to those of the first. The anode service life τ of the optimum spinel anode CoMn2O4/Ti is dependent on the current density, according to jλ τ = const. (λ = 1.7). Thus high current densities are precluded. The mechanism has been discussed in terms of a heterogeneous redox catalysis: surface Mn(VII) states are formed in a slow electrochemical step. In a subsequent fast chemical oxidation of the organic molecule the original reduced state is regenerated. This also explains the comparatively good service life of these anodes.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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