Hydrogen relative reactivity

The rate of addition depends on the concentration of both the butylene and the reagent HZ. The addition requires an acidic reagent and the orientation of the addition is regioselective (Markovnikov). The relative reactivities of the isomers are related to the relative stabiUty of the intermediate carbocation and are isobutylene 1 — butene > 2 — butenes. Addition to the 1-butene is less hindered than to the 2-butenes. For hydrogen bromide addition, the preferred orientation of the addition can be altered from Markovnikov to anti-Markovnikov by the presence of peroxides involving a free-radical mechanism. 

The hydrogen-deuterium exchange rates for 1,2-dimethylpyrazolium cation (protons 3 and 5 exchange faster than proton 4 Section 4.04.2.1.7(iii)) have been examined theoretically within the framework of the CNDO/2 approximation (73T3469). The final conclusion is that the relative reactivities of isomeric positions in the pyrazolium series are determined essentially by inductive and hybridization effects. 

A wide variety of electrophilic species can effect aromatic substitution. Usually, it is a substitution of some other group for hydrogen that is of interest, but this is not always the case. Scheme 10.1 lists some of the specific electrophilic species that are capable of carrying out substitution for hydrogen. Some indication of the relative reactivity of the electrophiles is given as well. Most of these electrophiles will not be treated in detail until Part B. Nevertheless, it is important to recognize the very broad scope of electrophiUc aromatic substitution. 

Another experiment of the competition type involves the comparison of the reactivity of different atoms in the same molecule. For example, gas-phase chlorination of butane can lead to 1- or 2-chlorobutane. The relative reactivity k /k of the primary and secondaiy hydrogens is the sort of information that helps to characterize the details of the reaction process. 

The value of k /k can be determined by measuring the ratio of the products 1-chlorobutane 2-chlorobutane during the course of the reaction. A statistical correction must be made to take account of the fact that the primary hydrogens outnumber the secondaiy ones by 3 2. This calculation provides the relative reactivity of chlorine atoms toward the primary and secondary hydrogens in butane ... 

The best preparative results from autoxidation are encountered when only one relatively reactive hydrogen is available for abstraction. The oxidation of isopropylbenzene (cumene) is carried out on an industrial scale, with the ultimate products being acetone and phenol ... 

It is postulated that hydrogen-bonded cyclic transition states such as 62 or the analogous one involving H0CH2CH20 will be found to increase relative reactivity adjacent to the azine-nitrogen in aprotic solvents cf. also Sections II,E,2,e and II,F. 

The effect of hydrogen bonding to nuclear substituents in transition states is reviewed in Sections I,D, 2,b, and II, E. Relative reactivity at different ring-positions is postulated to be alterable by hydrogen bonding of an azine-nitrogen to the solvent or to the reagent (Section II, B, 3 and III,B). However, there appears to be no kinetic data relevant to this postulate. 

Specific alterations of the relative reactivity due to hydrogen bonding in the transition state or to a cyclic transition state or to electrostatic attraction in quaternary compounds or protonated azines are included below (cf. also Sections II, B, 3 II, B, 5 II, C and II, F). A-Protonation is often reflected in an increase in JS and therefore the relative reactivity can vary with the significance of JS in controlling the reaction rate. Variation can also result from rate determination by the second stage of the SjjAr2 mechanism or from the intervention of thermodynamic control of product formation. Variation in the rate and in the reactivity pattern of polyazanaph-thalenes will result when nucleophilic substitution [Eq. (10)] occurs only on a covalent adduct (408) of the substrate rather than on its aromatic form (400). This covalent addition is prevented by any 4-... 

Problem 10.4 Taking the relative reactivities of 1°, 2°, and 3° hydrogen atoms into account, what product(s) would you expect to obtain from monochlorination of 2-methylbutane What would the approximate percentage of each product be (Don t forget to take into account the number of each sort of hydrogen.)... 

Rate Constants k (mmole min g ) of Isolated Reactions, and Relative Reactivities S from Competitive Reactions Obtained in the Hydrogenation of Aromatic Hydrocarbons... 

Purely parallel reactions are e.g. competitive reactions which are frequently carried out purposefully, with the aim of estimating relative reactivities of reactants these will be discussed elsewhere (Section IV.E). Several kinetic studies have been made of noncompetitive parallel reactions. The examples may be parallel formation of benzene and methylcyclo-pentane by simultaneous dehydrogenation and isomerization of cyclohexane on rhenium-paladium or on platinum catalysts on suitable supports (88, 89), parallel formation of mesityl oxide, acetone, and phorone from diacetone alcohol on an acidic ion exchanger (41), disproportionation of amines on alumina, accompanied by olefin-forming elimination (20), dehydrogenation of butane coupled with hydrogenation of ethylene or propylene on a chromia-alumina catalyst (24), or parallel formation of ethyl-, methylethyl-, and vinylethylbenzene from diethylbenzene on faujasite (89a). 

Fig. 8. Relationship between relative reactivities S and the ratios of the initial reaction rates rj°/VA° of alkylphenols to phenol in the hydrogenation on Ni-catalyst containing 8.4% (wt.) AUOa at 160°C and initial molar ratio of hydrogen to organic substances G = 19. Alkyl substituents in phenols Me—methyl, Et—ethyl, Pr—n-propyl, i-Pr— isopropyl, s-Bu—sec-butyl, t-Bu—terc-butyl.

Figure 1.9 Relative reactivity per hydrogen atom of indicated site towards t-...

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