Synthesis of nanocrystalline silicon carbide using the sol-gel technique

Highly disperse silicon carbide is synthesized using a hybrid method comprising the sol-gel step to provide the SiO₂-C starting mixture involving the formation of a transparent gel and carbothermal synthesis under relatively soft conditions, namely, at temperatures of 1200–1500°C under a dynamic vacuum. The elemental and phase compositions of the products and their thermal behavior in air are studied. A relationship is found to exist between the microstructure of the product, on the one hand, and the temperature and time of heat treatment, on the other.     

Multivariate optimization of the synthesis and of the microwave dissolution of biomorphic silicon carbide ceramics

Biomorphic silicon carbide ceramics are a new class of materials that are used for various industrial applications owing to its attractive properties. The efficiency of the synthesis and the partly extreme properties of the biomorphic ceramic depend decisively on the synthesis parameters and on the impurities of the final ceramic. In the present article the synthesis as well as the decomposition of these materials is optimized using a multivariate methodology for the design of experiments. Three variables (initial amount of Si, infiltration temperature and reaction time) were considered as factors in the synthesis optimization and six variables (digestion time, ramp time, microwave power, volumes of concentrated HF, HNO₃ and H₂SO₄) in the microwave dissolution optimization. Interactions, between analytical factors and their optimised levels were investigated using full factorial, Plackett–Burman and central composite designs. The synthesis parameters that found higher percentage of SiC (quantified by FTIR) and the digestion procedure that found higher concentrations of metals (Co, Cr and Ni, determined by FI-ETAAS) were considered the optimum.     

Diastereoselectivity in the Staudinger reaction: a useful probe for investigation of nonthermal microwave effects

The effect of microwave irradiation on the selectivity, especially stereoselectivity, is one of the most important issues in microwave-assisted organic reactions. The diastereoselectivity in Staudinger reactions involving the representative ketenes and the corresponding matched imines has been used as a probe to investigate carefully the existence of the specific nonthermal microwave effects. The results indicate that the microwave irradiation-controlled stereoselectivity in the Staudinger reaction is in fact the contribution of temperature. No specific nonthermal microwave effect was found in the Staudinger reaction.     

Atmosphere effects in the processing of silicon carbide and silicon oxycarbide thin films and coatings

Silicon carbide and silicon oxycarbide films were prepared from solutions of polycarbosilane and methyldimethoxysilane + tetraethoxysilane, respectively, and deposited on different substrates (Si wafers, stainless steel plates, sapphire and SiC fibers). The coatings were heated at different temperatures and in different atmospheres, such as regular grade argon, ultra high purity and argon vacuum. The films were characterized using different techniques (FT-IR, XRD, SIMS, Ellipsometry).The influence of the processing parameters (heat treatment temperature and atmosphere) on the final microstructure of the coatings is discussed in this article.     

A convenient strategy of dimerization by microwave heating and using 2,5-diketopiperazine as scaffold

A novel and convenient microwave-assisted dimerization of an active peptide compound using the DKPs as scaffold is described. The key reaction giving rise to the diketopiperazine scaffold is the intermolecular coupling. No epimerization was detected in the reactions used. Conventional and microwave heating of the reactions are compared. Synthesis by microwave irradiation gave the desired compounds in higher yields and in shorter reaction times than those obtained by conventional heating.     

Microwave-assisted asymmetric organocatalysis. A probe for nonthermal microwave effects and the concept of simultaneous cooling

A series of five known asymmetric organocatalytic reactions was re-evaluated at elevated temperatures applying both microwave dielectric heating and conventional thermal heating in order to probe the existence of specific or nonthermal microwave effects. All transformations were conducted in a dedicated reactor setup that allowed accurate internal reaction temperature measurements using fiber-optic probes. In addition, the concept of simultaneous external cooling while irradiating with microwave power was also applied in all of the studied cases. This method allows a higher level of microwave power to be administered to the reaction mixture and, therefore, enhances any potential microwave effects while continuously removing heat. For all of the five studied (S)-proline-catalyzed asymmetric Mannich- and aldol-type reactions, the observed rate enhancements were a consequence of the increased temperatures attained by microwave dielectric heating and were not related to the presence of the microwave field. In all cases, in contrast to previous literature reports, the results obtained either with microwave irradiation or with microwave irradiation with simultaneous cooling could be reproduced by conventional heating at the same reaction temperature and time in an oil bath. No evidence for specific or nonthermal microwave effects was obtained.     

Copper-catalyzed N-arylation of sulfonamides with aryl bromides and iodides using microwave heating

The copper-catalyzed N-arylation of sulfonamides with a variety of aryl bromides and iodides using microwave heating is described.     

Efficient ruthenium-catalyzed transfer hydrogenation/hydrogenation of 1,3-cycloalkanediones to 1,3-cycloalkanediols using microwave heating

A number of 1,3-cycloalkanediones were efficiently reduced to the corresponding diols in good yield by the use of a ruthenium catalyst, 2-propanol, and hydrogen gas under microwave heating.     

Ligand-free palladium catalysis of the Suzuki reaction in water using microwave heating

[reaction: see text] We report the ligand-free palladium catalysis of the Suzuki reaction in water using microwave heating. Our methodology uses low palladium loadings (0.4 mol %), is fast (5-10 min reaction time), and is useful for couplings involving boronic acids and aryl iodides, bromides, and chlorides.     

Design and application of a reflux modification for the synthesis of organometallic compounds using microwave dielectric loss heating effects

A commercially available microwave oven has been modified so that syntheses involving the refluxing of organic solvents can be safely and conveniently undertaken. The applications of this technique for accelerating the rates of reactions leading to the synthesis of some commonly used organometallic and coordination compounds are described.     

Combining optical lithography with rapid microwave heating for the selective growth of Au/Ag bimetallic core/shell structures on patterned silicon wafers

We demonstrate a novel approach for the production of patterned films of nanometer-sized Au/Ag bimetallic core/shell nanoparticles (NPs) on silicon wafers. In this approach, we first self-assembled monodisperse Au NPs, through specific Au...NH(2) interactions, onto a silicon substrate whose surface had been modified with a pattern of 3-aminopropyltrimethoxysilane (APTMS) groups to form a sandwich structure having the form Au NPs/APTMS/SiO(2). These Au NPs then served as seeds for growing the Au/Ag bimetallic core/shell NPs: we reduced silver ions to Ag metal on the surface of Au seeds under rapid microwave heating in the presence of sodium citrate. Energy-dispersive X-ray analysis confirmed that the Au/Ag bimetallic core/shell NPs grew selectively on the regions of the surface of the silicon wafer that had been patterned with the Au seeds. Scanning electron microscopy images revealed that we could synthesize well-scattered, high-density (>82%) thin films of Au/Ag bimetallic core/shell NPs through the use of this novel strategy. The patterned structures that can be formed are simple to produce, easily controllable, and highly reproducible; we believe that this approach will be useful for further studies of nanodevices and their properties.     

Efficient nucleophilic substitution of halopyridines using ethanol as solvent with microwave heating: synthesis of 2-aminoethylsulfanylpyridines

Abstract

Aminoethylsulfanylpyridine derivatives are important ligands used in medicinal chemistry, sensing devices, catalysis, and separation science. This paper reports the important finding that very high isolated yields of 2-aminoethyl-sulfanylpyridine isomers and substituted derivatives can be achieved by carrying out the synthesis with halopyridines using ethanol as both a solvent and reagent with microwave heating for short reaction times. Compared to the previous approaches employed for the synthesis of 2-aminoethylsulfanylpyridine derivatives, where yields can be very variable depending on the nature and position of the substituents in the halopyridine ring, the described procedures are more versatile and should be more broadly applicable to the nucleophilic substitution of halopyridines in general.     

Formation of 4-aminopyrimidines via the trimerization of nitriles using focused microwave heating

A series of substituted aliphatic nitriles have been trimerized to their corresponding pyrimidine structures under solvent-free conditions in the presence of catalytic quantities of potassium tert-butoxide using a focused microwave reactor. Multigram quantities of the corresponding 4-aminopyrimidines have been prepared in high yields and purity following a simple and scaleable protocol.     

Use of a silicon carbide multi-well plate in conjunction with microwave heating for rapid ligand synthesis, formation of palladium complexes, and catalyst screening in a Suzuki coupling

The preparation of a library of bis-imidazolium salts and corresponding palladium complexes is reported. These complexes are screened as catalysts in the Suzuki reaction between 4-bromoanisole and phenylboronic acid. Each step is performed in parallel using a 24-position silicon carbide plate and microwave heating. The plate allows for use of standard glass vials as reaction vessels. The ease and speed of operation show the potential for microwave heating in conjunction with the silicon carbide plate as a tool for catalyst screening.     

Fast, easy, clean chemistry by using water as a solvent and microwave heating: the Suzuki coupling as an illustration

Water is an excellent solvent for organic chemistry and microwave heating offers a very efficient way of heating reaction mixtures. In this article, by focusing on the Suzuki reaction, it is shown how these two methods, used alone or together, can impact modern synthetic chemistry, making reactions faster, easier and cleaner.     

A novel method for the synthesis of polysubstituted diaminobenzonitrile derivatives using controlled microwave heating

A novel, simple and efficient method for the synthesis of polysubstituted diaminobenzonitriles has been developed that involves reaction of 1,1,3-tricyano-2-aminopropionitrile with nitroolefins under controlled microwave irradiation conditions.     

Instrumental neutron activation analysis of silicon wafers using the silicon matrix as the comparator

For the instrumental neutron activation analysis of trace impurities in high purity silicon wafer, a modified single comparator method has been applied. The energy distribution of the neutrons at the irradiation position was measured using the two flux monitors, Au and Co, and elemental contents were calculated using the silicon matrix in the wafer as a comparator. This has advantage of reducing the cross contamination from an external monitor during sample preparation and irradiation, the uncertainties from the non-homogeneity of the neutron flux and the error on the weight of comparators. Determination limits for 49 elements were presented under the condition of 72 hours irradiation at a neutron flux of 3.7·10¹³ n·cm^-2·s^-1 and 4000 s measurement. The analytical results obtained by this method and the conventional single comparator method were compared and were found to agree well within 5%.     

Application of microwave dielectric loss heating effects for the rapid and convenient synthesis of organometallic compounds

Diolefin-rhodium(I) and -iridium(I) complexes have been synthesised in a sealed Teflon container by use of microwave heating. The products are obtained in excellent yields and in less than 1 minute compared with many hours by conventional reflux techniques. Furthermore, the sandwich cation [Rh(η-C₅H₅)₂]⁺ can be obtained directly from RhCl₃·χH₂O and C₅H₆ by this new technique.