ABSTRACT
The microwave-assisted hydrogenation of citral (3,7-dimethylocta-2,6-dienal) to citronellal with molecular hydrogen as the reducing agent was investigated. Several polar and non-polar solvents were screened and imidazolium-based ionic liquids were applied as modifiers for the palladium-containing porous glass catalysts (Pd/TP). The best results were obtained with N-ethyl-N'-methylimidazolium dicyanamide, N-ethyl-N'-methylimidazolium acetate, or N-ethyl-N'-methylimidazolium trifluoroacetate, which were used to prepare supported catalysts with an ionic liquid layer (SCILL) on Pd/TP by wet-impregnation. The influence of pressure and temperature when using these ionic liquid-containing catalysts, as well as their long-term stabilities, were examined. Working with microwave-assisted heating, high yields of citronellal were achieved under mild conditions within short reaction times. Catalyst characterization was carried out by means of BET measurements, X-ray photoelectron spectroscopy (XPS) and thermo-gravimetric analyses. The influences of the ionic liquid layer were derived from experiments carried out before and after the reactions.
Subject(s)
Glass/chemistry , Ionic Liquids/chemistry , Microwaves , Monoterpenes/chemistry , Acyclic Monoterpenes , Aldehydes/chemistry , Catalysis , Hydrogenation , Porosity , Pressure , Substrate Specificity , TemperatureABSTRACT
A Pd on porous glass catalyst system was used in the liquid-phase hydrogenation of terpenoid substrates with dihydrogen at room temperature and atmospheric pressure. A multitude of substances were hydrogenated selectively with yields of 90-100 %. In all experiments, only C--C, C--N, and N--N double bonds were hydrogenated. Studies revealed that carbonyl and aromatic double bonds are inert towards catalytic reduction with dihydrogen under the conditions employed. In some cases, hydrogenation was accompanied by isomerization, so that treatment of beta-pinene, for example, afforded isomeric alpha-pinene, which was subsequently hydrogenated to pinane.
Subject(s)
Glass/chemistry , Palladium/chemistry , Pressure , Catalysis , Hydrogenation , Particle Size , Porosity , Surface PropertiesABSTRACT
The catalytic activity of Pd supported on porous glass was studied for both Suzuki and Heck reactions under aerobic conditions, with particular focus on the Suzuki coupling. The reactions were carried out in water under microwave irradiation. The effects of the catalyst preparation process (calcination time and temperature), as well as the base, substrate, and boron compound used on the coupling reaction were investigated in relation to the reusability of the catalyst. Various bases promote the Suzuki coupling of phenylboronic acid with bromophenol very effectively resulting in quantitative conversion and excellent selectivity for the coupling product. However, most bases lead to deactivation of the catalyst after the first reaction cycle and the catalyst must be reactivated before reuse. Therefore, excellent conversions and selectivities for individual reactions are not sufficient to conclude if the chosen conditions are suitable for a given reaction, but resuits from recycling studies have to be considered also.
