Alkene also rate constants

The dependence of selectivity for dehydrogenation on the conversion of alkane shows that for the more selective catalysts known, the reaction proceeds with a sequential mechanism. The first step of the reaction is the breaking of a C—H bond of the alkane molecule, which is also the rate-limiting step. For these more selective catalysts, alkene is the primary product. Therefore, high selectivities can be obtained at low conversions. However, as the conversion increases, the selectivity decreases because of the secondary reaction of the alkene. The rate constant for the reaction of the alkene on the most selective catalyst is still about the same in magnitude as the rate constant for the activation of alkane. It is larger for the less selective catalysts. Thus the maximum yield of alkene among the catalysts known to date is still less than about 35%. To improve this yield, catalysts that react with alkene less rapidly than with alkane need to be found. 

The dependence of relative rates in radical addition reactions on the nucleophilicity of the attacking radical has also been demonstrated by Minisci and coworkers (Table 7)17. The evaluation of relative rate constants was in this case based on the product analysis in reactions, in which substituted alkyl radicals were first generated by oxidative decomposition of diacyl peroxides, then added to a mixture of two alkenes, one of them the diene. The final products were obtained by oxidation of the intermediate allyl radicals to cations which were trapped with methanol. The data for the acrylonitrile-butadiene... 

The pyridine ylide method also allows determination of the rate constants for the intermolecular reactions of carbenes with alkenes, alcohols, or other carbene... 

At about the same time, Mayr measured the rate of attack of various types of carbenium ions on alkenes by new and ingenious methods. His rate constants k2 for tertiary carbenium ions are ca. 4 orders of magnitude greater than the kp+ values recommended by this author [1], Despite detailed discussions between Mayr and the present writer, involving also a detailed examination of Mayr s methods, a reason for the discrepancy could not be discovered in the mid-1990s [2]. The purpose of the present paper is to suggest one, and thus to explain the discrepancy. 

Ru" (0)(N40)]"+ oxidizes a variety of organic substrates such as alcohols, alkenes, THE, and saturated hydrocarbons. " In all cases [Ru (0)(N40)] " is reduced to [Ru (N40)(0H2)] ". The C— H deuterium isotope effects for the oxidation of cyclohexane, tetrahydrofuran, 2-propanol, and benzyl alcohol are 5.3, 6.0, 5.3, and 5.9 respectively, indicating the importance of C— H cleavage in the transitions state. For the oxidation of alcohols, a linear correlation is observed between log(rate constant) and the ionization potential of the alcohols. [Ru (0)(N40)] is also able to function as an electrocatalyst for the oxidation of alcohols. Using rotating disk voltammetry, the rate constant for the oxidation of benzyl alcohol by [Ru (0)(N40)] is found to be The Ru electrocatalyst remains active when immobilized inside Nafion films. 

Confirmation was provided by the observation that the species produced by the photolysis of two different carbene sources (88 and 89) in acetonitrile and by photolysis of the azirine 92 all had the same strong absorption band at 390 nm and all reacted with acrylonitrile at the same rate (fc=4.6 x 10 Af s" ). Rate constants were also measured for its reaction with a range of substituted alkenes, methanol and ferf-butanol. Laser flash photolysis work on the photolysis of 9-diazothioxan-threne in acetonitrile also produced a new band attributed the nitrile ylide 87 (47). The first alkyl-substituted example, acetonitrilio methylide (95), was produced in a similar way by the photolysis of diazomethane or diazirine in acetonitrile (20,21). This species showed a strong absorption at 280 nm and was trapped with a variety of electron-deficient olefinic and acetylenic dipolarophiles to give the expected cycloadducts (e.g., 96 and 97) in high yields. When diazomethane was used as the precursor, the reaction was carried out at —40 °C to minimize the rate of its cycloaddition to the dipolarophile. In the reactions with unsymmetrical dipolarophiles such as acrylonitrile, methyl acrylate, or methyl propiolate, the ratio of regioisomers was found to be 1 1. 

In addition to electron-transfer reactions such as (39)—(42), N03 can also react in solution with a variety of organics. For example, addition to the double bond in alkenes is quite fast, with rate constants of the order of 109 L mol-1 s-1 at room temperature the reactions... 

Phenyl azide was also found to react with alkenes in TFA (Scheme 11). The reaction was assumed to go via an aziridinium ion generated from attack of the alkene on the nitrenium ion because of the overall /rans-addition to the alkene noted in product 29. An alternative Sn2 mechanism was disfavored because phenyl azide decomposes at 21 °C in 50 vol% cyclohexene/TFA with an almost identical first-order rate constant as in 50vol% benzene/TFA even though cyclohexene is a considerably stronger nucleophile than benzene. ... 

The overall course of reaction depends on the relative rate constants for the various secondary radical processes. Aliphatic ketones are often photoreduced to secondary alcohols (4.121, but although there are interesting features in the stereochemistry of the reduction, the method is not a worthwhile alternative to thermal reduction using hydride reagents, except in cases where the substrate is sensitive to basic conditions. Photoaddition of methanol is promoted in the presence of titaniurnfiv) chloride, both for acyclic and cyclic (4.33) ketones the titanium involvement probably starts in the early steps of the reaction, but the detailed mechanism is not known. Addition may also be a major pathway when cyclohexene is used as hydrogen source (4.341 unlike many other simple alkenes, cydohexene does not readily give oxetanes by photocycloaddition (see p. 126). 

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