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Synergistic Nanostructured MnOx/TiO2 Catalyst for Highly Selective Synthesis of Aromatic Imines
This work reports the development of a synergistic nanostructured MnOx/TiO2 catalyst, with highly dispersed MnOx nanoparticles (4.5±1 nm) on shape-controlled TiO2 nanotubes (8–11 nm width and 120–280 nm length), for selective synthesis of valuable aromatic imines at industrially important conditions. Pristine TiO2 nanotubes exhibited 97 % imine selectivity at a 38.3 % benzylamine conversion, whereas very low imine selectivity was obtained over commercial TiO2 materials, indicating the catalytic significance of shape-controlled TiO2 nanotubes. The MnOx nanoparticle/TiO2 nanotube (10 wt% Mn) catalyst calcined at 400 °C showed the best activity with 95.6 % benzylamine conversion and 99.9 % imine selectivity. This catalyst exhibited good recyclability for four times and is effective for converting numerous benzylamines into higher yields of imines. The high catalytic performance of MnOx/TiO2 nanotubes was attributed to higher number of redox sites (Mn3+), high dispersion of Mn species, and shape-controlled structure of TiO2, indicating that this catalyst could be a promising candidate for selective oxidation reactions. © 2021 The Authors. ChemCatChem published by Wiley-VCH GmbH
Synthesis of novel chemicals from cardanol as a product of cashew nutshell processing
The conversion of the worldwide chemical production from fossil to sustainable resources is currently one of the most urgent tasks for the chemical industry. Based on this approach cardanol, a mixture of phenols with C15-chains as substituents is produced in some countries of the tropical zone from the processing of cashew nutshells. The paper reports the specific transformation of the aromatic moiety in this cheap material, and thus, the development of a novel route to potential useful green bifunctional chemicals in gram scale. Accordingly, cardanol was converted successfully in three steps into hexane-1,6-diols. The evaluation of appropriate synthesis methods and suitable conditions for each of these reaction steps is presented as an essential topic of these investigations. The target compounds synthesized in the reaction sequence are potential building blocks for future biomass-based chemicals and monomers for green polymeric materials, surfactants, and lubricants.
Catalytic β-Bromohydroxylation of Natural Terpenes: Useful Intermediates for the Synthesis of Terpenic Epoxides
In a one-step procedure, various ß-bromoalcohols were synthesized from natural terpenes in good to excellent yields. Using different catalysts, the reaction was carried out at room temperature, with H 2 O as nucleophile and N-bromosuccinimide as a bromine source under mild reaction conditions. The synthesized ß-bromoalcohols were subsequently converted in situ to the corresponding epoxides in good yields. © 2019 Saadia Oubaassine et al.
Abschlussbericht zum Verbundvorhaben "Neuartige Polymere auf Basis von Triglyceriden" : Darstellung der erzielten Ergebnisse für die Teilvorhaben mit den Partnern ; Teilvorhaben 1: Entwicklung von Katalysatoren und Herstellung neuer Monomere, Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LITKAT) ; Teilvorhaben 2: Herstellung der Polyamide und Polyurethane, Fraunhofer-Institut für Chemische Technologie (ICT) ; Teilvorhaben 3: Entwicklung von Verfahren zur Herstellung von Monomeren für Kunststoffe aus plfanzlichen Ölsäuren, Evonik Oxeno GmbH (Oxeno) ; Teilvorhaben 4: Herstellung der Polyamide sowie Bewertung, Evonik Degussa GmbH (High Performance Polymers [HPP]) ; Teilvorhaben 5: Herstellung der Polyurethane sowie Bewertung und Dokumentation, Rampf Ecosystems GmbH & Co KG ; Laufzeit des Vorhabens/Berichtszeitraum: 01.10.2008 bis 31.12.2011
[no abstract available]
Heterogeneously Catalysed Oxidative Dehydrogenation of Menthol in a Fixed-Bed Reactor in the Gas Phase
For the first time, the oxidative dehydrogenation of (−)-menthol to (−)-menthone and (+)-isomenthone in a marketable quality was carried out in a continuous gas phase reactor as a sustainable process using molecular oxygen as green oxidant and solid catalysts which do not contaminate the product mixture and which are easily to remove. The diastereomeric purity remained largely unchanged. Three types of catalysts were found to be very active and selective in the formation of menthone and isomenthone: AgSr/SiO2, CuO distributed on a basic support and RuMnCe/CeO2, where Ru, Mn and Ce exist in an oxidized state. The best overall yield of menthon/isomenthone obtained with an Ag-based catalyst was 58 % at 64 % selectivity, with a Cu-based catalyst 41 % at 51 % selectivity and with a Ru-based catalyst 68 % at 73 % selectivity. Reaction conditions were widely optimized. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Selective Wacker type oxidation of a macrocyclic diene to the corresponding monounsaturated ketone used as fragrance
A selective reaction method for the efficient conversion of an isomeric mixture of 1,9-cyclohexadecadiene (1,9-CHDD) to the corresponding monounsaturated cyclohexadec-8-en-1-one (8-CHD) is described. 8-CHD was synthesized via Wacker type oxidation at room temperature using a highly electrophilic in situ formed dicationic palladium species. Isomerisation of the diene and over-oxidation of the substrate could be nearly suppressed by suitable reaction control, which has a positive effect on selectivity. The utilization of molecular oxygen as a green oxidant and environmentally benign iron(iii) salts as co-catalysts was successfully applied. This reaction strategy is promising to overcome the low overall reactivity of internal olefins in Wacker type oxidations. In addition, larger scale experiments showed further potential for industrial application. This journal is © 2019 The Royal Society of Chemistry.