Microwave-assisted processes

Bromo-4-chloro-lH-pyrazolo[3,4-d]pyrimidine could be easily fimc-tionalized at C-3 and C-4 in a one-pot two-step microwave-assisted process (Scheme 34) [55]. Ding and Schultz reported that nucleophilic substitution of the addition-elimination type at the C-4 position with amines and anilines smoothly occurred under acidic conditions in dioxane upon irradiation... 

This is a problem that has been reported by several researchers in other cya-nation methods on heteroaromatic halides. (Hetero)aryl chlorides have also been tackled via in situ halogen exchange to (hetero)aryl bromides followed by sequential cyanation (Scheme 71). For this microwave-assisted process an equimolar amount of NiBr2 and a two-fold excess of NaCN were used. The only heteroaromatic chloride tested was 2-chloropyridine. Although the procedures described involve the use of significant amounts of nickel salts, a clear advantage is that the reactions can be performed in air. Moreover, the cyanat-ing reagents are easily removed since they are water soluble. 

The selectivity of the catalyst is of major importance in the case of chlorinated VOCs the oxidation products should not contain even more harmful compounds than the parent-molecule, for example, formation of dioxins should be avoided. In addition, the minimization of CI2 and maximization of HCl in a product gas should be achieved [61]. These are just a few examples of why researchers are continuing the search for VOC oxidation catalysts as well as new reactor concepts. The new possibilities include, for example, utilization of nanosized gold catalysts in the oxidation of sulfur-containing VOCs and microwave-assisted processes where combination of adsorption and oxidation is used in low-concentration VOC oxidation [62, 63]. 

In liquid-solid extraction (LSE) the analyte is extracted from the solid by a liquid, which is separated by filtration. Numerous extraction processes, representing various types and levels of energy, have been described steam distillation, simultaneous steam distillation-solvent extraction (SDE), passive hot solvent extraction, forced-flow leaching, (automated) Soxh-let extraction, shake-flask method, mechanically agitated reflux extraction, ultrasound-assisted extraction, y -ray-assisted extraction, microwave-assisted extraction (MAE), microwave-enhanced extraction (Soxwave ), microwave-assisted process (MAP ), gas-phase MAE, enhanced fluidity extraction, hot (subcritical) water extraction, supercritical fluid extraction (SFE), supercritical assisted liquid extraction, pressurised hot water extraction, enhanced solvent extraction (ESE ), solu-tion/precipitation, etc. The most successful systems are described in Sections 3.3.3-3.4.6. Other, less frequently... 

Principles and Characteristics Pare et al. [475] have patented another approach to extraction, the Microwave-Assisted Process (MAP ). In MAP the microwaves (2.45 GHz, 500 W) directly heat the material to be extracted, which is immersed in a microwave transparent solvent (such as hexane, benzene or iso-octane). MAP offers a radical change from conventional sample preparation work in the analytical laboratory. The technology was first introduced for liquid-phase extraction but has been extended to gas-phase extraction (headspace analysis). MAP constitutes a relatively new series of technologies that relate to novel methods of enhancing chemistry using microwave energy [476]. 

LED Light emitting diode MAP Microwave-assisted Process ... 

Another metal-catalyzed microwave-assisted transformation performed on a polymer support involves the asymmetric allylic malonate alkylation reaction shown in Scheme 12.4. The rapid molybdenum(0)-catalyzed process involving thermostable chiral ligands proceeded with 99% ee on a solid support. When TentaGel was used as as support, however, the yields after cleavage were low (8-34%) compared with the corresponding solution phase microwave-assisted process (monomode cavity) which generally proceeded in high yields (>85%) [30],... 

T0272 Environment Canada, Microwave-Assisted Process... 

T0272 Environment Canada, Microwave-Assisted Process T0277 Environmental Remediation Consultants, Inc., Biointegration T0282 Environmental Soil Management, Inc., Low-Temperature Thermal Desorption T0286 Environmental Treatment and Technologies Corporation, Methanol Extraction Process... 

The Microwave-Assisted Process (MAP ) technology uses microwaves, and solvents that are relatively transparent to microwaves, to extract chemicals from various matrices based on the temperature differential between the solvent and the target compound. According to the developers, the technology is applicable to soils and wastes containing polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), total petroleum hydrocarbons (TPH), and other organic compounds. 

Demaree, R. S. 2001. Microwave-assisted processing of biological samples for scanning electron microscopy. In Microwave Techniques and Protocols (R.T. Giberson and R.S. Demaree eds.), pp. 209-216. Humana Press, Totowa, NJ. 

Comment. Although a 20% solution of the nitrohydrazone in polyphosphoric acid could be cyclized by heating,71 (c) the use of polyphosphoric acid is not particularly desirable. The microwave-assisted process could be worthy of development if there was no other, more economical, way of accessing this specific indole derivative—for example, by nitration of the more readily prepared 1,2,3,4-tetrahydro-1 -oxo- (3 -carboline.71 (a)... 

Comment. Superficially, this one-pot microwave-assisted process looks very attractive. However, in this case, development of a microwave-assisted process will depend on comparison with classical procedures.74 For instance, Ganboa and... 

Palomo75 report that various aromatic aldehydes can be converted to nitriles in 94-97% yield by refluxing the aromatic aldehyde, hydroxylamine hydrochloride, and magnesium sulfate in toluene or xylene, with p-toluencsulfonic acid as catalyst for 1.5 to 3 hr. The microwave-assisted process may prove better for aliphatic aldehydes and may be made even more attractive if the above process conditions could be refined to reduce or eliminate NMP—for instance, if both aldehyde and nitrile form a homogeneous liquid at the reaction temperature. 

This microwave-assisted reaction was carried out on a 3-g scale in a glass vessel placed in a bath of alumina/magnetite. The anthraquinone (m.p. 284°C) produced was collected as it sublimed from the reactor. Further, o-benzoylbenzoic acid was added and the reaction repeated. The main advantage of the microwave-assisted reaction lies in the recycling of the catalyst. The yield in the conventional heating process falls to 50% after four uses of catalyst, whereas in the microwave-assisted process the yield is still 84% after fifteen uses. 

Should the economics of the above-described new process favor a switch from the present AIC process (see Case Study 2) to one based on dihydrohypoxanthine new investment might be justified in new production equipment.81 A switch to the microwave option versus the conventional heating option would depend on the outcome of process optimization work on both. If a rapid clean reaction in near-quantitative yield were realized by optimizing the microwave conditions, then it would prove worthwhile to engineer a simple continuous flow reactor for further development work. The case in favor of adopting the microwave-assisted process would be further enhanced if the solution from the microwave reactor could be used directly in the next process step (thus eliminating the need for isolation equipment). 

Before applications are dealt with, the main variables governing microwave-assisted processes and the parameters characterizing specific microwave treatments are examined. The applications discussed include not only microwave-assisted digestion and extraction — which are the two most widely implemented and hence those with the highest potential interest to readers — but also others of special significance to solid sample treatment such as microwave-assisted drying, distillation and protein hydrolysis. Finally, some safety recommendations on the use of microwave equipment are made. 

Performance in microwave-assisted processes depends on a number of variables including the microwave power output, exposure time, solvent and sample size used. However, specific treatments such as digestion are additionally dependent upon factors such as the digesting acid, pressure and its relationship to temperature in closed-vessel systems, the residence time in flow systems, the number of cycles used in an FMAS extractor, etc., all of which should be optimized for each specific situation. 

Temperature is a key variable in most analytical processes. In microwave-assisted processes, it plays a prominent role and affects the rate of some reactions, the degradation of thermolabile species and the solubilization of some substances, among others. A number of devices have been developed for monitoring or even controlling the temperature, some of which are commented on in Section 5.3. 

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