Dielectric heating solids

Use of specific forms of radiant energy, infrared, ultraviolet, dielectric heating, etc., can allow specific separations to be made. The separation of clear and colored grains of glass and the separation of different metals are possible apphcations of the thermoadhesive method being considered in the field of solid-waste processing. 

Abstract Current microwave-assisted protocols for reaction on solid-phase and soluble supports are critically reviewed. The compatibility of commercially available polymer supports with the relatively harsh conditions of microwave heating and the possibilities for reaction monitoring are discussed. Instrmnentation available for microwave-assisted solid-phase chemistry is presented. This review also summarizes the recent applications of controlled microwave heating to sohd-phase and SPOT-chemistry, as well as to synthesis on soluble polymers, fluorous phases and functional ionic liquid supports. The presented examples indicate that the combination of microwave dielectric heating with solid- or soluble-polymer supported chemistry techniques provides significant enhancements both at the level of reaction rate and ease of purification compared to conventional procedures. 

Chemicals and the containment materials for chemical reaction do not interact equally with the commonly used microwave frequencies for dielectric heating and consequently selective heating may be achieved. Specifically, it is possible to cool the outside of the vessel with a coolant that is transparent to microwaves (solid C02 or liquid N2) and thereby have cold walls that still allowthe microwave energy to penetrate and heat the reactants, which are microwave active, in the vessel. Also for solid-state reactions contamination from the crucible walls may be minimised. 

Westman, J., An efficient combination of microwave dielectric heating and the use of solid-supported triph-enylphosphine for Wittig Reaction, Org. Lett., 2001, 3745—3747. 

The combination of microwave-assisted chemistry and solid-phase synthesis applications is a logical consequence of the increased speed and effectiveness offered by microwave dielectric heating. While this technology is heavily used in the pharmaceutical and agrochemical research laboratories already, a further increase in the use of microwave-assisted solid-phase synthesis both in industry and in academic laboratories can be expected. This will depend also on the availability of modern microwave instrumentation specifically designed for solid-phase chemistry, involving for example dedicated vessels for bottom filtration techniques. 

Dabirmanesh, Q. and Roberts, R.M.G., The synthesis of iron sandwich complexes by microwave dielectric heating using a simple solid C02-cooled apparatus in an unmodified commercial microwave Oven, /. Organomet. Chem., 1993, 460, C28. 

Moulded articles can be thermally treated to improve the physical properties, particularly the notched Izod impact strength, but removal of the volatile by-products of the solid-phase polymerisation is a greater problem than for fibres and films 112). Use of internal dielectric heating has been suggested as a means of avoiding limitation of further polymerisation to the surface. 

Abstract Recent developments in the microwave-assisted synthesis of heterocycles are surveyed with the focus on diversity-oriented multi-component and multi-step one-pot procedures. Both solution- and solid-phase as well as polymer-supported methodologies for the preparation of libraries of heterocycles are reviewed. Advantages of microwave dielectric heating are highlighted by comparison with conventional thermal conditions. 

To address the purification issue, which frequently is a bottle-neck in the fast microwave chemistry, a solid-phase catch and release methodology was utilized in a two-component, two-step synthesis of l-alkyl-4-imidazolecarboxylates [45]. In the first step, a collection of isonitriles 25 was immobilized onto a solid support by the reaction with the commercially available N-mclhyl aminomethylated polystyrene 26. Subsequent treatment with various amines brought about simultaneous derivatization and release of the desired imidazoles 27 back into solution. Significantly, only derivatized material was released from the resin, thus ensuring high purity of the desired product. Both steps of the reaction were substantially accelerated by microwave dielectric heating, resulting in the overall reaction time reduction from 60 hours to 70 minutes (Scheme 18). 

A microwave-assisted one-pot approach towards 2,4,5-trisubstituted oxazoles employed a hypervalent iodine (III) catalyst to bring about the reaction of ketones, 1,3-diketones and /3-keto-carboxylic acid derivatives with amides [75]. Microwave dielectric heating was also successfully utilized in a solid-supported, solvent-free synthesis of 2-phenyl-oxazol-5-ones (azlac-tones) [76] as well as in a solution phase synthesis of isomeric 2-phenyl-oxazol-4-ones (oxalactims) [77]. 

Aminoquinolines 62 have been prepared in a two-step, one-pot, three-component reaction of 2-azidobenzophenones, secondary amines and arylac-etaldehydes [110]. The microwave-assisted reaction proceeded via the initial formation of enamines 59. Subsequent addition of 2-azidobenzophenones 60 afforded the triazoline intermediates 61, which underwent thermal rearrangement and cyclocondensation to furnish 2-aminoquinolines 62 (Scheme 41). Direct comparison with conventional thermal conditions demonstrated the superiority of microwave dielectric heating in terms of yields (73% vs. 31% of heterocycle 63 after 10 min at 180 °C). Furthermore, the formation of by-products due to decomposition of azide 60 was diminished in the microwave-assisted synthesis. Purification of the products was achieved using solid-phase extraction techniques. 

The Friedlander annulation is one of the most straightforward approaches towards poly-substituted quinolines. Thus, a 22-membered library of quinolines was synthesized in a TsOH-catalyzed cyclocondensation-dehydration of 2-aminoaryl ketones and 2-aminoarylaldehydes with ketones in a household microwave oven (with power control) under solvent-free conditions [112]. It was observed that the Friedlander reaction occurred readily also in an oil-bath (at 100 °C). To compare the conventional and dielectric heating conditions precisely, a purpose-built monomode microwave system with temperature control was employed instead of the household oven. The experiments at 100 °C under otherwise identical conditions demonstrated that the dielectric heating protocol was only slightly faster. Products were isolated by a simple precipitation-neutralization sequence (in the case of solid products) or neutralization-extraction for oily or low melting point products (Scheme 43). 

Epoxy adhesives should be 100 percent solids so as to eliminate the possibility of gassing and bubbles occurring in the bond line. However, dielectric heating is often used in the furniture industry to drive off water quickly from water-based adhesive emulsions. Water, being a polar material, heats rapidly in a microwave field, as every cook knows. 

After coupling of (hetero)aroyl chlorides 7 and terminal alkynes 4, hydrazines 29, and acetic acid are added and reacted in the same reaction vessel. Best results for the formation of pyrazoles 30 are obtained by dielectric heating in the micro-wave oven at 150°C for 10 min in the presence of methanol. Pyrazoles 30 are obtained in good to excellent yields, predominantly as colorless crystalline solids (Scheme 21) [113]. This concept has also been applied to the nonregioselective synthesis of 3,5-disubstituted pyrazoles 30 (R = H) upon conductive heating in the cyclocondensation step [114]. 

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