David Obermayer

Sintered Silicon Carbide: A New Ceramic Vessel Material for Microwave Chemistry in Single-Mode Reactors

Silicon carbide (SiC) is a strongly microwave absorbing chemically inert ceramic material that can be utilized at extremely high temperatures due to its high melting point and very low thermal expansion coefficient. Microwave irradiation induces a flow of electrons in the semiconducting ceramic that heats the material very efficiently through resistance heating mechanisms. The use of SiC carbide reaction vessels in combination with a single-mode microwave reactor provides an almost complete shielding of the contents inside from the electromagnetic field. Therefore, such experiments do not involve electromagnetic field effects on the chemistry, since the semiconducting ceramic vial effectively prevents microwave irradiation from penetrating the reaction mixture. The involvement of electromagnetic field effects (specific/nonthermal microwave effects) on 21 selected chemical transformations was evaluated by comparing the results obtained in microwave-transparent Pyrex vials with experiments performed in SiC vials at the same reaction temperature. For most of the 21 reactions, the outcome in terms of conversion/purity/product yields using the two different vial types was virtually identical, indicating that the electromagnetic field had no direct influence on the reaction pathway. Due to the high chemical resistance of SiC, reactions involving corrosive reagents can be performed without degradation of the vessel material. Examples include high-temperature fluorine-chlorine exchange reactions using triethylamine trihydrofluoride, and the hydrolysis of nitriles with aqueous potassium hydroxide. The unique combination of high microwave absorptivity, thermal conductivity, and effusivity on the one hand, and excellent temperature, pressure and corrosion resistance on the other hand, makes this material ideal for the fabrication of reaction vessels for use in microwave reactors.

Nanocatalysis in continuous flow: supported iron oxide nanoparticles for the heterogeneous aerobic oxidation of benzyl alcohol

Investigations on heterogeneous iron catalysis in the selective aerobic oxidation of a primary alcohol are presented. Continuous flow technology was used in combination with an iron oxide nanoparticle catalyst stabilized in a mesoporous aluminosilicate support (“flow nanocatalysis”) as a process intensification tool to maximize catalyst efficiency. Using 5 mol% 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a co-catalyst, up to 42% benzyl alcohol as a simple model substrate was selectively converted to benzaldehyde in a single pass of the reactor. Full conversion was achieved by continuous recirculation, simulating an extension of the catalyst bed. ICPMS analysis indicated that the catalyst is highly stable and does not leach under the investigated conditions, providing solid evidence for the participation of a heterogeneous iron species in the catalytic cycle.

Microwave-assisted and continuous flow multistep synthesis of 4-(pyrazol-1-yl)carboxanilides.

A series of 4-(pyrazol-1-yl)carboxanilides active as inhibitors of canonical transient receptor potential channels were synthesized in an efficient three-step protocol using controlled microwave heating. The general synthetic strategy involves condensation of 4-nitrophenylhydrazine with appropriate 1,3-dicarbonyl building blocks, followed by reduction of the nitro group to the amine, which is then amidated with carboxylic acids. Compared to the conventional protocol a dramatic reduction in overall processing time from ~2 days to a few minutes was achieved, accompanied by significantly improved product yields. In addition, the first two steps in the synthetic pathway were also performed under continuous flow conditions providing similar isolated product yields. As an alternative to the three-step protocol, a novel two-step route to the desired 4-(pyrazol-1-yl)carboxanilides was devised involving condensation of 4-bromophenylhydrazine with appropriate 1,3-dicarbonyl building blocks, followed by Pd-catalyzed Buchwald-Hartwig amidation with carboxylic acid amides.

Safe Generation and Synthetic Utilization of Hydrazoic Acid in a Continuous Flow Reactor

Hydrazoic acid (HN3) was used in a safe and reliable way for the synthesis of 5-substitued-1H-tetrazoles and for the preparation of N-(2-azidoethyl)acylamides in a continuous flow format. Hydrazoic acid was generated in situ either from an aqueous feed of sodium azide upon mixing with acetic acid, or from neat trimethylsilyl azide upon mixing with methanol. For both processes, subsequent reaction of the in situ generated hydrazoic acid with either organic nitriles (tetrazole formation) or 2-oxazolines (ring opening to β-azido-carboxamides) was performed in a coil reactor in an elevated temperature/pressure regime. Despite the explosive properties of HN3, the reactions could be performed safely at very high temperatures to yield the desired products in short reaction times and in excellent product yields. The scalability of both protocols was demonstrated for selected examples. Employing a commercially available benchtop flow reactor, productivities of 18.9 g/h of 5-phenyltetrazole and 23.0 g/h of N-(1-azido-2-methylpropan-2-yl)acetamide were achieved.

Electromagnetic simulations of microwave heating experiments using reaction vessels made out of silicon carbide

There is a growing body of literature which reports the use of silicon carbide vessels to shield reaction mixtures during microwave heating. In this paper we use electromagnetic simulations and microwave experiments to show that silicon carbide vessels do not exclude the electric field, and that dielectric heating of reaction mixtures will take place in addition to heat transfer from the silicon carbide. The contribution of dielectric heating and heat transfer depends on the dielectric properties of the mixture, and the temperature at which the reaction is carried out. Solvents which remain microwave absorbent at high temperatures, such as ionic liquids, will heat under the direct influence of the electric field from 30-250 degrees C. Solvents which are less microwave absorbent at higher temperatures will be heated by heat-transfer only at temperatures in excess of 150 degrees C. The results presented in this paper suggest that the influence of the electric field cannot be neglected when interpreting microwave assisted synthesis experiments in silicon carbide vessels.

Insights into the microwave-assisted preparation of supported iron oxide nanoparticles on silica-type mesoporous materials

A detailed investigation on the microwave-assisted preparation of iron oxide nanoparticles on mesoporous Si-SBA-15 support is described, employing a dedicated single-mode microwave reactor with internal reaction temperature control. Using iron(II) chloride as iron precursor and ethanol as solvent, extensive optimization studies demonstrate that after 3–5 min at 150–200 °C well-defined 3–5 nm iron oxide nanoparticles (Fe2O3, hematite phase) are obtained. In contrast to the chosen reaction temperature, reaction time and stirring efficiency are of critical importance in the preparation of these supported nanoparticles. Extended reaction times (>10 min) lead to a significant proportion of larger aggregates while inefficient stirring also produces low quality nanoparticles as a result of poor dispersion and delivery of the iron precursor to the mesoporous support. Carefully executed control studies between microwave and conventionally heated experiments applying otherwise identical reaction conditions demonstrate that the quality of the obtained supported iron oxide nanoparticles is largely independent on the heating mode, as long as a the exact same temperature profile can be maintained.

Versatile low-loaded mechanochemically synthesized supported iron oxide nanoparticles for continuous flow alkylations

A novel and highly versatile mechanochemically synthesized low-loaded (0.25 wt.%) supported iron oxide nanocatalyst has been demonstrated to be highly active and selective for the production of o- and p-benzylmethylbenzene (preferentially) C–C alkylated products in the continuous flow alkylation of toluene with benzyl chloride as compared to the etherification product (dibenzyl ether) observed in the alkylation of toluene with benzyl alcohol. The low quantities of highly accessible iron oxide nanoparticles on the external surface of an aluminosilicate support provided versatile acidic sites that were able to promote both the alkylation of toluene with benzyl alcohol and benzyl chloride. ICP-MS analysis revealed that the catalyst is highly stable and does not significantly leach under the investigated conditions, providing solid evidence of an iron-catalysed heterogeneous protocol.