Mechanistic selectivity

Catalysts differ in their ability to promote double-bond migration and cis-trans isomerization, in their thermodynamic and mechanistic selectivities in diene hydrogenation and in their tendencies to catalyze 1,2-, 3,4-, or 1,4-addition34. 

It is clear that all three types of selectivity are relevant to catalytic hydrogenation reactions and from a consideration of the reaction scheme for alkyne hydrogenation (Fig. 4), it can be deduced that all three factors may be operative simultaneously. Clearly, the selectivity for the formation of the alkene relative to alkane will depend upon a number of factors. If both the alkene and the alkane are formed during one residence of the parent molecule on the surface, the selectivity will depend upon the relative values of k, and k2 (Type II selectivity) and upon the ratio kjk4 (Type II selectivity). Since both of these depend upon the specific properties of the catalyst, they have been termed the mechanistic selectivity factor [38], Once the alkene is produced, the system contains another potential adsorbate and Type I selectivity must be taken into account. It... 

A general scheme of hydrogenation of 1,3-butadiene, the rake mechanism, is given in Scheme 7. Two kinds of selectivity for the intermediate butenes can be defined. Selective formation of butenes can be expected if > 4 (mechanistic selectivity). On the other hand, if k /k- > kj,/k, adsorption of the diene prevents the readsorption of butenes and hence the consecutive hydrogen addition cannot take place (thermodynamic... 

Column headings D = fractional dispersion, d = size (nm) S subscripts < 6 2-methylpentane 3 = 3-methylpentane n = n-hexane S = mechanistic selectivity (%). EUROPT-l (6% Pt/SiOj) ... 

CAMEO Assessment. Using starting materials and reaction conditions as input, CAMEO predicts the products of organic reactions using a mechanistic selection of algorithms for a wide variety of reaction modules (i.e., Carbenoid, Basic ucleophilic,... 

A topic of current interest is that of methane activation to give ethane or selected oxidation products such as methanol or formaldehyde. Oxide catalysts are used, and there may be mechanistic connections with the Fischer-Tropsch system (see Ref. 285). 

This chapter introduces the experimental work described in the following chapters. Some mechanistic aspects of the Diels-Alder reaction and Lewis-acid catalysis thereof are discussed. This chapter presents a critical survey of the literature on solvent ejfects on Diels-Alder reactions, with particular emphasis on the intriguing properties of water in connection with their effect on rate and selectivity. Similarly, the ejfects of water on Lewis acid - Lewis base interactions are discussed. Finally the aims of this thesis are outlined. 

The first example of enantioselective catalysis of a Diels-Alder reaction was reported in 1979 . Since then, an extensive set of successful chiral Lewis-acid catalysts has been prepared. Some selected examples will be presented here together with their mechanistic interpretation. For a more complete... 

It can be concluded, as already stated above, that the diminution in intermolecular selectivity observed in these nitrations with nitronium salts in organic solvents does not of itself require any special mechanistic considerations as regards the process of substitution. 

The mechanistic complexity of hydroboration-oxidation stands m contrast to the simplicity with which these reactions are carried out experimentally Both the hydrobo ration and oxidation steps are extremely rapid reactions and are performed at room tern perature with conventional laboratory equipment Ease of operation along with the fact that hydroboration-oxidation leads to syn hydration of alkenes and occurs with a regio selectivity opposite to Markovmkov s rule makes this procedure one of great value to the synthetic chemist... 

A spectacular example of selective deliydiogenation in the steroid ring system (42) has been attributed to stereoelectronic effects (31) the yield is 80%. Several related steroids also show this chemistry. An extensive review containing many additional examples and a mechanistic discussion is available (23). 

Equation 1 is referred to as the selective reaction, equation 2 is called the nonselective reaction, and equation 3 is termed the consecutive reaction and is considered to proceed via isomerization of ethylene oxide to acetaldehyde, which undergoes rapid total combustion under the conditions present in the reactor. Only silver has been found to effect the selective partial oxidation of ethylene to ethylene oxide. The maximum selectivity for this reaction is considered to be 85.7%, based on mechanistic considerations. The best catalysts used in ethylene oxide production achieve 80—84% selectivity at commercially useful ethylene—oxygen conversion levels (68,69). 

Correlations of nucleation rates with crystallizer variables have been developed for a variety of systems. Although the correlations are empirical, a mechanistic hypothesis regarding nucleation can be helpful in selecting operating variables for inclusion in the model. Two examples are (/) the effect of slurry circulation rate on nucleation has been used to develop a correlation for nucleation rate based on the tip speed of the impeller (16) and (2) the scaleup of nucleation kinetics for sodium chloride crystalliza tion provided an analysis of the role of mixing and mixer characteristics in contact nucleation (17). Pubhshed kinetic correlations have been reviewed through about 1979 (18). In a later section on population balances, simple power-law expressions are used to correlate nucleation rate data and describe the effect of nucleation on crystal size distribution. 

In this section a selection procedure will be developed for injection moulding, since this process is used for the widest range of materials. The choice available for other processes such as, for example, compression moulding, filament winding and vacuum forming, is much more restricted. The approach described will be less mechanistic than the systems described in the two previous sections, requiring the prospective user to be aware of the properties of the various materials available. Because the approach is somewhat different, it would be instructive to run it parallel to the above processes and compare the results. 

At this point, attention can be given to specific electrophilic substitution reactions. The kinds of data that have been especially useful for determining mechanistic details include linear ffee-energy relationships, kinetic studies, isotope effects, and selectivity patterns. In general, the basic questions that need to be asked about each mechanism are (1) What is the active electrophile (2) Which step in the general mechanism for electrophilic aromatic substitution is rate-determining (3) What are the orientation and selectivity patterns ... 

A highly selective photochemical chlorination of esters, amides, and alcohols can be effected in 70%-90% H2SO4 using A-chlorodialkylamines as chlorinating agents. Mechanistic studies indicate that a chain reaction is involved ... 

Since the stereochemical course of a catalytic hydrogenation is dependent on several factors, " an understanding of the mechanism of the reaction can help in the selection of optimal reaction conditions more reliably than mere copying of a published recipe . In the first section the factors which can influence the product stereochemistry will be discussed from a mechanistic viewpoint. In subsequent sections the hydrogenation of various functional groups in the steroid ring system will be considered. In these sections both mechanistic and empirical correlations will be utilized with the primary emphasis being placed on selective and stereospecific reactions. 

It is hoped that these volumes will be useful not only to the chemist who wishes to carry out synthesis in the steroid field, but also to the broader group of organic chemists who are interested in carrying out selective and stereo-chemically defined reactions, as well as protective chemistry on extraneous functional groups, during a broad range of synthetic applications. The chapter on the introduction of deuterium and by inference tritium into steroids was included because of the importance of this technique in mechanistic and metabolic studies both in the steroid and nonsteroid field. 

The standard state chosen for the calculation of controls its magnitude and even its sign. The standard state is established when the concentration scale is selected. For most solution kinetic work the molar concentration scale is used, so A values reported by different workers are usually comparable. Nevertheless, an important chemical question is implied Because the sign of AS may depend upon the concentration scale used for the evaluation of the rate constant, which concentration scale should be used when A is to serve as a mechanistic criterion The same question appears in studies of equilibria. The answer (if there is a single answer) is not known, though some analyses of the problem have been made. Further discussion of this issue is given in Section 6.1. 

It must be appreciated that the selection of the best model—that is, the best equation having the form of Eq. (6-97)—may be a difficult problem, because the number of parameters is a priori unknown, and different models may yield comparable curve fits. A combination of statistical testing and chemical knowledge must be used, and it may be that the proton inventory technique is most valuable as an independent source capable of strengthening a mechanistic argument built on other grounds. 

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