Solvents selective heating

This symposium book provides examples of process development in the pharmaceutical industry by several experts in the field. Chapter 1 is concerned mostly with the general aspect of scale-up such as solvent selection, heating, cooling, and stirring. Chapter 2 is a brilliant... 

While most polymer/additive analysis procedures are based on solvent or heat extraction, dissolution/precipita-tion, digestions or nondestructive techniques generally suitable for various additive classes and polymer matrices, a few class-selective procedures have been described which are based on specific chemical reactions. These wet chemical techniques are to be considered as isolated cases with great specificity. 

These results provide clear evidence for the existence of selective heating effects in MAOS involving heterogeneous mixtures. It should be stressed that the standard methods for determining the temperature in microwave-heated reactions, namely with an IR pyrometer from the outside of the reaction vessel, or with a fiber-optic probe on the inside, would only allow measurement of the average bulk temperature of the solvent, not the true reaction temperature on the surface of the solid reagent. 

A selective heating in liquid/liquid systems was exploited by Strauss and coworkers in a Hofmann elimination reaction using a two-phase water/chloroform system (Fig. 2.10) [32]. The temperatures of the aqueous and organic phases under micro-wave irradiation were 110 and 55 °C, respectively, due to the different dielectric properties of the solvents (Table 2.3). This temperature differential prevented decomposition of the final product. Comparable conditions would be difficult to obtain using traditional heating methods. A similar effect has been observed by Hallberg and coworkers in the preparation of /3,/3-diarylated aldehydes by hydrolysis of enol ethers in a two-phase toluene/aqueous hydrochloric acid system [33],... 

To elucidate the cause of the microwave-induced enhancement of the rate of this reaction in more detail the transformation of 2-t-butylphenol was performed at low temperatures (up to -176 °C). At temperatures below zero the reaction did not proceed under conventional conditions. When the reaction was performed under micro-wave conditions in this low temperature region, however, product formation was always detected (conversion ranged from 0.5 to 31.4%). It was assumed that the catalyst was superheated or selectively heated by microwaves to a temperature calculated to be more than 105-115 °C above the low bulk temperature. Limited heat transfer in the solidified reaction mixture caused superheating of the catalyst particles and this was responsible for initiation of the reaction even at very low temperatures. If superheating of the catalyst was eliminated by the use of a nonpolar solvent, no reaction products were detected at temperatures below zero (see also Sect. 10.3.3). 

Snyder and coworkers followed a completely different path to canthin-6-one (Fig. 23). Earlier they had shown that indole-substituted 1,24-triazine 66 could be heated in refluxing triisopropylbenzene (bp = 232 °C) to give /3-carboline 67 via an intramolecular cycloaddition/cycloreversion reaction [58]. Selective oxidation of 67 at C-6 was achieved through the use of triethylbenzylammonium permanganate [59]. Success of the reaction proved to be very sensitive to the solvent chosen. Heating 67 for 4 h at 70 °C in a 5 1 mixture of dichloromethane and acetic acid gave a 65% yield of 63, yet use of increasing amounts of dichloromethane slowed the reaction down (no reaction occurred in pure dichloromethane), while use of pure acetic acid led to an intractable mixture. 

In catalysis applications, the tunable solvent properties result in a variety of effects, such as controllable component and catalyst solubilities. Moreover, it is possible that kinetic rates are affected by both temperature and pressure effects, equilibrium constants are shifted in favor of the desired products, and selectivity and yields are increased by manipulating the solvent s dielectric constant or by controlling the temperature in highly exothermic reactions through an adjustment of the solvent s heat capacity [18-23]. 

To produce pure hydrogen, the carbon dioxide must be removed. The gas passes through a carbon dioxide removal system, which contains a chemical solvent that selectively absorbs the carbon dioxide as the gas passes through the solvent.12 Heat then is added to the solvent to discharge the carbon dioxide. The regenerated solvent is returned to the system to continue the removal of carbon dioxide. 

Just in the USA during 2001, the man-made plastic fiber industry had over 90 plants with sales of 13 billion and employed about 45,000 people. Fabrication processes are diverse both in technology and equipment design. They have common steps that include preparation of reactants, polymerization, plastic recovery, plastic extrusion, and supporting operations. In some preparation operations, solvents are used to dissolve or dilute monomer and reactants. Solvents are also used to facilitate the transportation of the reaction mixture throughout the plant, to improve heat dissipation during the reaction, and to promote uniform mixing. Solvent selection is optimized to increase monomer... 

Extractive distillation is evaluated as an alternative to ordinary distillation for the separation of propylene-propane mixtures. Particular attention is given to the necessary compromises between different design factors solvent concentration within the primary column, solvent selectivity, solvent loss, etc. A major expense is associated with the sensible heat requirements of the circulating solvent process modifications so as to minimize this expense are discussed. The process analysis explores combinations of solvent selectivity and other solvent properties which might make extractive distillation attractive. It appears that in almost all cases extractive distillation offers no advantage compared with ordinary distillation. Only in special cases may circumstances warrant extractive distillation. External factors favoring the use of extractive distillation are identified. 

Figure 9. Effect of solvent selectivity on annual costs at constant propane activity coefficient (process with heat exchange...

When carrying out the solvent selection experiments you must always cool the solution after heating. Do not assume that if the compound is insoluble in the cold solvent and dissolves when heated, it will always precipitate on cooling. 

To carry out a single-solvent recrystallization (Box 13.3) you must get the compound into solution and this is achieved by suspending it in the appropriate cold solvent, found in the solvent selection process, and then heating the mixture to dissolve the soUd. The equipment used will depend on the boiling point of the solvent, its flammability and toxicity. Some general systems are shown in Table 13.2. 

Model includes Stoichiometry, 100% yield (ideal) Conversion, selectivity, auxiliary, catalyst, solvent, byproduct heat of reaction Shortcut process models, simple property data Rigorous process modeis, non-ideaiity, reaction kinetics, detaiied property data... 

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