Selectivity in complex reactions

Equation (19-22) indicates that, for a nominal 90 percent conversion, an ideal CSTR will need nearly 4 times the residence time (or volume) of a PFR. This result is also worth bearing in mind when batch reactor experiments are converted to a battery of ideal CSTRs in series in the field. The performance of a completely mixed batch reactor and a steady-state PFR having the same residence time is the same [Eqs. (19-5) and (19-19)]. At a given residence time, if a batch reactor provides a nominal 90 percent conversion for a first-order reaction, a single ideal CSTR will only provide a conversion of 70 percent. The above discussion addresses conversion. Product selectivity in complex reaction networks may be profoundly affected by dispersion. This aspect has been addressed from the standpoint of parallel and consecutive reaction networks in Sec. 7. 

Changes in the product selectivity in complex reactions occurring in zeolites resulting from coke deposition have been evaluated (38,91) in terms of the effect of... 

Several caveats should be mentioned at this point. When there are multiple reactions, the half-life in Equation 1.54 is the shortest half-life that affects yield and selectivity. In complex reaction schemes, there may be some important fast reactions that are mixing dependent even thought the overall reaction is slow. An example is a catalyst that may react with itself if not rapidly diluted. Equations 1.59 and... 

The primary feature of heterogeneous systems is that the purely physical problem of transporting reactants and products between phases is appended to the chemical transformation. Stated alternatively, a physical rate process (transport) occurs in series with a chemical rate process (reaction). As nature would have it, often these rates are of similar magnitudes and the overall behavior of the reaction system depends on their relative magnitude, not only in terms of the net kinetics of transformation but also with regard to the product selectivity in complex reactions. 

Bubble columns, in which the liquid is the continuous phase, are used for slow reactions. Drawbacks with respect to packed columns are the higher pressure drop and the important degree of axial and radial mixing of both the gas and the liquid, which may be detrimental for the selectivity in complex reactions. On the other hand they may be used when the fluids carry solid impurities that would plug packed columns. In fact, many bubble column processes involve a finely divided solid catalyst that is kept in suspension, like the Rheinpreussen Fischer-Tropsch synthesis, described by Kolbel [1], or the former I. G. Farben coal hydrogen process, or vegetable oil hardening processes. Several oxidations are carried out in bubble columns the production of acetaldehyde from ethylene, of acetic acid from C4 fractions, of vinylchloride from ethylene by oxychlorina-tion, and of cyclohexanone from cyclohexanol. 

Enhancing the selectivity in complex reaction schemes may be the biggest challenge on the shoulders of the chemists and chemical engineers. Sustainable production of desired chemicals requires improved material and energy economies. After the conclusion of Chapter 2, it must have been obvious that low selectivity results in wasting valuable raw materials. Additional energy penalties are due in terms of separation costs. Hence, selective manufacture of the desired chemicals is imperative in a world where sustainability is the primary concern. 

Macromixing models play an essential role in modeling and scale-up of chemical reactors. Besides, the areas where micromixing is a controlling factor, are now clearly identified selectivity in complex reactions involving at least a fast step between unmixed reactants, crystallization and precipitation reactions, oxygen supply in fermentors. .. this list is not exhaustive. 

Chelucci et al. [41] synthesized further chiral terpyridines derived from (-)-yd-pinene, (-i-)-camphor, and (-l-)-2-carene and tested their ability to chelate copper or rhodium for the asymmetric cyclopropanation of styrene. The copper catalysts were poorly efficient and selective in this reaction. The corresponding rhodium complexes led to the best result (64% ee) with the ligand derived from (-l-)-2-carene (ligand 33 in Scheme 17). 

Essentially, there are no general guidelines for preliminary model selection for complex reactions. Mechanistic studies are the best basis for model formulation. Literature data and indications clear to experienced organic chemists will certainly be the most helpful. Studies on individual reactions are always recommended, but for the complex reactions involved in fine chemistry such an opportunity is rather a rare case. 

The corresponding permethylzirconocene moiety is complexed by triynes RC = C—C = C—C=CR through two triple bonds in a refashion and complex 107 is obtained. Detailed NMR investigations have revealed a sliding of the permethylzirconocene along the triyne backbone 108 [55], This result is important because it shows there to be a lot of species in the mixture this is the reason for the low selectivity in some reactions. 

Dauben et al. (15) applied the Aratani catalyst to intramolecular cyclopropanation reactions. Diazoketoesters were poor substrates for this catalyst, conferring little asymmetric induction to the product, Eq. 10. Better results were found using diazo ketones (34). The product cyclopropane was formed in selectivities as high as 77% ee (35a, n = 1). A reversal in the absolute sense of induction was noted upon cyclopropanation of the homologous substrate 34b (n = 2) using this catalyst, Eq. 11. Dauben notes that the reaction does not proceed at low temperature, as expected for a Cu(II) precatalyst, but that thermal activation of the catalyst results in lower selectivities (44% ee, 80°C, PhH, 35a, n = 1). Complex ent-11 may be activated at ambient temperature by reduction with 0.25 equiv (to catalyst) DIBAL-H, affording the optimized selectivities in this reaction. The active species in these reactions is presumably the aluminum alkoxide (33). Dauben cautions that this catalyst slowly decomposes under these conditions. 

In recent years, interest in radical-based transformations of allenes has been renewed for two major reasons. First, a number of useful intramolecular additions of carbon-centered radicals to 1,2-dienes have been reported, which allowed syntheses of complex natural product-derived target molecules to be accomplished in instances where other methods have failed to provide similar selectivities. Further, a large body of kinetic and thermochemical data has become accessible from results of experimental and theoretical investigations in order to predict selectivities in addition reactions to allenes more precisely. Such contributions originated predominantly from (i) studies directed towards an understanding of the incineration process,... 

Adsorption of Ag on the surface of PdO is also an interesting option offered by colloidal oxide synthesis. Silver is a well-known promoter for the improvement of catalytic properties, primarily selectivity, in various reactions such as hydrogenation of polyunsaturated compounds." The more stable oxidation state of silver is -F1 Aquo soluble precursors are silver nitrate (halide precursors are aU insoluble), and some organics such as acetate or oxalate with limited solubility may also be used." Ag" " is a d ° ion and can easily form linear AgL2 type complexes according to crystal field theory. Nevertheless, even for a concentrated solution of AgNOs, Ag+ does not form aquo complexes." Although a solvation sphere surrounds the cation, no metal-water chemical bonds have been observed. 

The TMEDA complex of a-lithiobenzyl iV,iV-diisopropylcarbamate was found to be configurationally stable on the microscopical scale in the Hoffmann test . The (—)-sparteine complex 222 has moderate configurational stability on the macroscopic scale, which could not been brought to useful selectivities in substitution reactions . As... 

Metal complexes of bis(oxazoline) ligands are excellent catalysts for the enantioselective Diels-Alder reaction of cyclopentadiene and 3-acryloyl-l,3-oxa-zolidin-2-one. This reaction was most commonly utilized for initial investigation of the catalytic system. The selectivity in this reaction can be twofold. Approach of the dienophile (in this case, 3-acryloyl-l,3-oxazolidin-2-one) can be from the endo or exo face and the orientation of the oxazolidinone ring can lead to formation of either enantiomer R or S) on each face. The ideal catalyst would offer control over both of these factors leading to reaction at exclusively one face (endo or exo) and yielding exclusively one enantiomer. Corey and co-workers first experimented with the use of bis(oxazoline)-metal complexes as catalysts in the Diels-Alder reaction between cyclopentadiene 68 and 3-acryloyl-l,3-oxazolidin-2-one 69 the results are summarized in Table 9.7 (Fig. 9.20). For this reaction, 10 mol% of various iron(III)-phe-box 6 complexes were utilized at a reaction temperature of —50 °C for 2-15 h. The yields of cycloadducts were 85%. The best selectivities were observed when iron(III) chloride was used as the metal source and the reaction was stirred at —50 °C for 15 h. Under these conditions the facial selectivity was determined to be 99 1 (endo/exo) with an endo ee of 84%. 

Although iV-acyloxazolidinones 88 and iV-acylthiazolidinethiones 90 lead to an anti aldol, the respective products 89 and 91 present a different anti configuration. Consequently, the corresponding derived magnesium enolates exhibit the opposite face selection in these reactions. On the basis of previous results involving enolates of various metal complexes such as boron, titanium, lithium or sodium enolates, the (Z)-metal enolate... 

The site-selective reduction of a,co-dienes, in which the two double bonds are differentiated only by the presence of an allylic substituent, is a challenging task. A pentamethylyttrocene complex that is extremely selective in hydrogenating terminal alkenes exhibits good selectivity in this reaction 142... 

The oxidative method is often conducted on enol (or enolate) derivatives and a simplified mechanism is shown in Scheme 71. Initial chemical or electrochemical oxidation gives an electrophilic radical (68 that may be free or metal-complexed) that is relatively resistant to further oxidation. Addition to an alkene now gives an adduct radical (69) that is more susceptible to oxidation. Products are often derived from the resulting intermediate cation (70) by inter- or intra-molecular nucleophilic capture or by loss of a proton to form an alkene. The concentration and oxidizing potential of the reagent help to determine the selectivity in such reactions. 

Nickel catalyst complexed with unfunctionalized chelating bisphosphine ligands, (R,R) norphos (75) 151 ] and 76 [ 19,52], also induced a high selectivity in the reaction shown in Scheme 8F.5 (Table 8F. 1, entries 38-39). The results reported with other phosphine ligands 33, 77-80 [30,53-56] are summarized in the Table 8F.1 (entries 40-44). 

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