Kinetic product distribution

For the kinetically controlled formation of 1,3-disubstituted tetrahydro-P-carbolines, placing both substituents in equatorial positions to reduce 1,3-diaxial interactions resulted in the cw-selectivity usually observed in these reactions." Condensation reactions carried out at or below room temperature in the presence of an acid catalyst gave the kinetic product distribution with the cw-diastereomer being the major product observed, as illustrated by the condensation of L-tryptophan methyl ester 41 with benzaldehyde. At higher reaction temperatures, the condensation reaction was reversible and a thermodynamic product distribution was observed. Cis and trans diastereomers were often obtained in nearly equal amounts suggesting that they have similar energies."... 

The kinetic product distribution appears to be determined by steric factors ex-substitution favors quinonemethide formation ring substitution favors a,cx-coupling. However, since quinonemethide formation is reversible, the only iso table product is often that from a,a-coupling. 

All that is required is to locate transition states leading to the two products, decide which is lower in energy and use the energy difference between the two to obtain the kinetic product distribution. Hartree-Fock 3-2IG calculations should be sufficient to perform these tasks. One should also be on the lookout for clues in the structures and conformations of the two transition states as to why one is preferred over the other. 

The kinetic product distribution can be further shifted in excess reagent to get organozirconium derivatives with high regioselectivity. Even subtle steric differences such as in 2-pentyne ensure high selectivity [Eq. (6.77), a]. As Eq. (6.77) demonstrates, hydrozirconation of alkynes is an exclusive syn process. 

Vitamin E is effective as an antioxidant in arachidonate autoxidation, trapping the kinetic peroxyl radical product before cyclization can occur. Adding vitamin E in arachidonate autoxidation results in reducing radical cyclization products and forming the kinetic product distribution, six simple trans, cis diene hydroperoxides. 

The lack of dependence on ionic strength in the first reaction indicates that it occurs between neutral species. Mono- or dichloramine react much slower than ammonia because of their lower basicities. The reaction is faster with CI2 because it is a stronger electrophile than with HOCl The degree of chlorination increases with decreasing pH and increasing HOCINH mol ratio. Since chlorination rates exceed hydrolysis rates, initial product distribution is deterrnined by formation kinetics. The chloramines hydrolyze very slowly and only to a slight extent and are an example of CAC. 

The reactions are highly exothermic. Under Uquid-phase conditions at about 200°C, the overall heat of reaction is —83.7 to —104.6 kJ/mol (—20 to —25 kcal/mol) ethylene oxide reacting (324). The opening of the oxide ring is considered to occur by an ionic mechanism with a nucleophilic attack on one of the epoxide carbon atoms (325). Both acidic and basic catalysts accelerate the reactions, as does elevated temperature. The reaction kinetics and product distribution have been studied by a number of workers (326,327). 

Mechanism. The thermal cracking of hydrocarbons proceeds via a free-radical mechanism (20). Siace that discovery, many reaction schemes have been proposed for various hydrocarbon feeds (21—24). Siace radicals are neutral species with a short life, their concentrations under reaction conditions are extremely small. Therefore, the iategration of continuity equations involving radical and molecular species requires special iategration algorithms (25). An approximate method known as pseudo steady-state approximation has been used ia chemical kinetics for many years (26,27). The errors associated with various approximations ia predicting the product distribution have been given (28). 

As a practical method, designers have employed other methods such as / -pentane conversion as a key component, kinetic severity factor (31), or molecular collision parameter (32) to represent severity. Alternatively, molecular weight of the complete product distribution has been used to define conversion (A) for Hquid feeds. 

Chemical reactions often yield entirely different product distributions depending on the conditions under which they are carried out. In particular, high temperatures and long reaction times favor the most stable ( thermodynamic ) products, while low temperatures and short reaction times favor the most easily formed ( kinetic ) products. 

Many authors have observed that the cis-trans ratio of the products of the metathesis reaction is equal to the thermodynamic equilibrium value. This suggests that the reaction is not highly stereoselective. However, under certain conditions the product distribution is influenced by kinetic factors. For instance, it proves to be possible to prepare from cyclopentene... 

It is clear from the results that there is no kinetic isotope effect when deuterium is substituted for hydrogen in various positions in hydrazobenzene and 1,1 -hydrazonaphthalene. This means that the final removal of hydrogen ions from the aromatic rings (which is assisted either by the solvent or anionic base) in a positively charged intermediate or in a concerted process, is not rate-determining (cf. most electrophilic aromatic substitution reactions47). The product distribution... 

The problems of distinguishing H+ produced from H2 by electron impact from the product of dissociative charge transfer reactions between He + and H2 can be studied by determining the kinetic energy distribution in the product H+ (6). The reaction He+ + H2 is exothermic by 6.5 e.v. if the products are atoms or atomic ions. If the reaction is studied with HD substituted for H2, then the maximum kinetic energy that can be deposited in the D + is approximately 2.16 e.v. On the other hand, D + can be produced by electron impact with 5.5 e.v. kinetic energy. If a retarding potential is applied at the repeller in the ion-source of a mass spectrometer, then it is possible to obtain curves related to the kinetic... 

Thermodynamic Versus Kinetic Control of Product Distributions. 228... 

Similar anomalous distributions are observed in other thermal product mixtures. A commercial soft caramel made by heating sucrose and 0.1% acetic acid to 160°C contained 18% of a mixture of di-D-fructose dianhydrides.94 fi-D-Fru/-1,2 2,1 - 3-D-Fru/(now assigned as a-D-Fru/-l,2 2,l -a-D-Fru/83), ot-D-Fru/-1,2 2,1 -p-D-Fru/(5), ot-D-Frup-1,2 2,l -0-D-Fnjp (4), ot-D-Fru/-l,2 2,1 - 3-D-Frup (1), and p-D-Fru/-l,2 2,3 - 3-D-Fru/ (2) were found in the ratio 4 12 1 6 2. The first three of these, constituting 68% of the mixture, are considered to be kinetic products. The authors commented on this, but did not offer any explanation. Notice, however, that the preparation of such commercial caramels commences with heating of an acidic aqueous solution of sucrose, which almost certainly results in hydrolysis. Hence, the final dianhydrides are probably derived from the reaction of fructose, rather than sucrose. 

A number of Diels Alder reactions have been investigated in supercritical media and some of them will be illustrated. Most of the research has been focused on the influence of the pressure, which greatly influences the density of the fluid, on the kinetic aspects and on the product distribution of the reaction. 

Since the transition state for alcohol oxidation and ketone reduction must be identical, the product distribution (under kinetic control) for reducing 2-butanone and 2-pentanone is also predictable. Thus, one would expect to isolate (R)-2-butanol if the temperature of the reaction was above 26 °C. On the contrary, if the temperature is less than 26 °C, (S)-2-butanol should result in fact, the reduction of... 

The thermodynamic product distribution in the Friedel-Crafts methylation (Scheme 20) is in contrast to the kinetic distribution. The reaction kinetically shows the ortho and para orientations. Thermodynamic stabilities of the products prefer the meta isomer as a major product. 

It was suggested that this change in product distribution was due to the existence of an equilibrium between two types of complex, viz., a cr-butenyl-pentacyanocobaltate(III) and a 7r-butenyltetracyanocobaltate(III) 107, 109). However, further study of the kinetics and product distribution suggested the presence of two o-bonded complexes, viz., cr-but-l-en-3-yl and a-but-2-en-l-yl 24a). Direct evidence for the existence of a cyanide-dependent equilibrium between the a- and rr-bonded organocyanide complexes has been obtained from NMR studies of the complex prepared by the reaction of allyl halides with Co—H 109) (see also Section V,C). Both butadiene and crotyl chloride react with Co—H to give the same... 

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