Isomerization of cycloalkanes

The isomerization of cycloalkanes over SbF5-intercalated graphite can be achieved at room temperature without the usual ring opening and cracking reactions, which occur at higher temperatures and lower acidities.110 In the presence of excess hydrocarbon after several hours, the thermodynamic equilibrium is reached for the isomers. Interconversion between cyclohexane (20) and methylcyclopentane (21) yields the thermodynamic equilibrium mixture [Eq. (5.46)]. 

The skeletal isomerization of cycloalkanes with more than six carbon atoms, that is cycloheptane, cyclooctane, cyclodecane, and cyclododecane, was performed over S04/Zr02 in the liquid phase at 50 °C. 

I d like to comment on the experimental methodology used to study the reaction. Herman Bloch points out that Pines always was careful and used the best available techniques to do his work. The use of high vacuum technique here illustrates this point. The isomerization of cycloalkanes was fully studied by several students collaborating with Pines (8-17). Again they used high vacuum technique. And toward the end of this research carbon 14 labeling was done. Again, this illustrated Bloch s point use of the best techniques. 

Levsen, K. Isomerization of Hydrocarbon Ions. II. Octenes and Isomeric Cycloalkanes. Collisional Activation Study. Org. Mass Spectrom. 1975,10, 55-63. 

Cycloalkanes. Methylene reacts with the C—H bonds of cycloalkanes to form excited methyl cycloalkanes, which may undergo uni-molecular isomerization or dissociation (dissociation would constitute an abstraction reaction) or may be collisionally deactivated. 

The platforming catalyst was the first example of a reforming catalyst having two functions.43 44 93 100-103 The functions of this bifunctional catalyst consist of platinum-catalyzed reactions (dehydrogenation of cycloalkanes to aromatics, hydrogenation of olefins, and dehydrocyclization) and acid-catalyzed reactions (isomerization of alkanes and cycloalkanes). Hyrocracking is usually an undesirable reaction since it produces gaseous products. However, it may contribute to octane enhancement. n-Decane, for example, can hydrocrack to C3 and C7 hydrocarbons the latter is further transformed to aromatics. 

Catalytic reforming has become the most important process for the preparation of aromatics. The two major transformations that lead to aromatics are dehydrogenation of cyclohexanes and dehydrocyclization of alkanes. Additionally, isomerization of other cycloalkanes followed by dehydrogenation (dehydroisomerization) also contributes to aromatic formation. The catalysts that are able to perform these reactions are metal oxides (molybdena, chromia, alumina), noble metals, and zeolites. 

Mechanism. The proven acidity of the effective alkane isomerization catalysts suggests that carbocations are involved in acid-catalyzed alkane isomerization. Such a mechanism was first proposed by Schmerling and coworkers54 on the basis of the pioneering ideas of Whitmore55 for the skeletal isomerization of alkanes and cycloalkanes in the presence of aluminum chloride and a trace of olefin or other promoter. Subsequently these concepts were used to explain the mechanism of the acid-catalyzed isomerizations in general. 

The acid-catalyzed isomerization of cycloalkenes usually involves skeletal rearrangement if strong acids are used. The conditions and the catalysts are very similar to those for the isomerization of acyclic alkenes. Many alkylcyclohexenes undergo reversible isomerization to alkylcyclopentenes. In some cases the isomerization consists of shift of the double bond without ring contraction. Side reactions, in this case, involve hydrogen transfer (disproportionation) to yield cycloalkanes and aromatics. In the presence of activated alumina cyclohexene is converted to a mixture of 1-methyl- and 3-methyl-1-cyclopentene 103... 

Adsorption modes and hydrogenolysis were also correlated with other metal-catalyzed reactions. Gault noticed striking similarities in product distributions of isomerization and ring opening of cycloalkanes. Kinetic and tracer studies provided useful data252 268 to arrive at the conclusion that a common surface intermediate is... 

Hydrogenative ring opening of cycloalkanes is also a well-studied area.16 252 253 289-292 Mainly cyclopropanes and cyclopentanes were studied, since three- and five-membered adsorbed carbocyclic species are believed to be intermediates in metal-catalyzed isomerization of alkanes (see Section 4.3.1). Ring-opening reactivity of different ring systems decreases in the order cyclopropane > cyclobutane > cyclopentane > cyclohexane.251 Cyclopropane and its substituted derivatives usually react below 100°C. 

During studies of the hydrogenolysis and isomerization of the 2-Me-oxa-cycloalkanes on transition metal catalysts, it was found that different metals have different regioselectivities (refs 1,2). On Cu and Ni catalysts, primarily the C-0 bond adjacent to the substituent is split, leading to the formation of a primary alcohol or aldehyde (ref. 3), while on Pt and Pd catalysts mainly the more distant C-0 bond undergoes cleavage (ref. 4) yielding a secondary alcohol or ketone (Scheme 1). 

Irradiation of methylcyclopropylketone (Formula 311) causes isomerization to 3-penten-2-one (Formula 312) (124). This reaction appears to be limited to acyl cyclopropanes, since acyl cycloalkanes with larger rings undergo photochemical fission to acyl radicals and cycloalkyl radicals (105). The photoisomerization of the bicyclic ketone (Formula 313) to Formula 314 (125) is analogous to the isomerization of Formula 311. 

Cracking and disproportionation in the reaction of hexane could be suppressed by the addition of cycloalkanes (cyclohexane, methylcyclopentane, cyclopentane).101 Furthermore, 3-methylpentane and methylcyclopentane also reduced the induction period. These data indicate that reactions are initiated by an oxidative formation of alkene intermediates. These maybe transformed into alkenyl cations, which undergo cracking and disproportionation. When there is intensive contact between the phases ensuring effective hydride transfer, protonated alkenes give isomerization products. 

The microstructure of the discussed cycloaliphatic polymers concerns the cis-trans geometrical isomerism of the rings and the relative stereochemistry between the rings. A modified Bovey m-r nomenclature [507] provides a useful description of the microstructure of poly(methylene-l,3-cycloalkane)s, where capital letters (M for mesogenic, R for racemic) denote the stereochemistry of the rings and lower case letters ( m and r) denote the relative stereochemistry between the rings [503], Therefore, cA-isotactic, tram-isotactic, cA-syndiotactic and tram-syndiotactic cyclopolymers may be formed. As in many other cases, 13C NMR spectroscopy reveals information about both the tacticity of the polymer and the ratio of cis to treins rings. 

Summary Rules for Naming Alkanes 94 3-4 Physical Properties of Alkanes 95 3-5 Uses and Sources of Alkanes 97 3-6 Reactions of Alkanes 99 3-7 Structure and Conformations of Alkanes 100 3-8 Conformations of Butane 104 3-9 Conformations of Higher Alkanes 106 3-10 Cycloalkanes 107 3-11 Cis-trans Isomerism in Cycloalkanes 109 3-12 Stabilities of Cycloalkanes Ring Strain 109 3-13 Cyclohexane Conformations 113... 

Cis-trans isomerism in cycloalkanes. Like alkenes, cycloalkane rings are restricted from free rotation. Two substituents on a cycloalkane must be either on the same side (cis) or on opposite sides (trans) of the ring. 

Define or identify each of the following terms (a) organic chemistry, (b) total bond order, (c) condensed formula, (d) structural formula, (e) fine formula, (/) hydrocarbon, (g) alkane, (h) aUcene, (/) alkyne, j) aromatic hydrocarbon, (k) saturated, (1) delocalized double bond, (m) isomerism, (n) cycloalkane, (o) radical, (p) functional group, (q) alcohol, (r) ether, (s) aldehyde, (f) ketone, (u) carbonyl group, and (v) ester. 

MF5 and MCI5 are strongly electrophilic see Electrophile and Electrophilic Reaction) and catalyze Friedel-Crafts reactions. The HF/TaFs system is a superacid catalyst and has been used in the selective acid-catalyzed isomerization and hydrogenolysis of cycloalkanes. Oligomerization and polymerization of alkynes with Nb and Ta halides as catalysts have been reported see Oligomerization Polymerization by Homogeneous Catalysis) ... 

The isomerization of open-chain alkanes with more than six carbon atoms gives isobutane as the main product, together with disproportionated materials, even though the reaction proceeds by the monomolecular pathway [144]. On the other hand, for cyclic alkanes the monomolecular process with preservation of the cyclic structure seems to be the most probable, judging from the results for cyclohexane. The absence of isobutane in the products indicates that the reaction path does not involve open-chain intermediate species. Therefore, it is of interest to try cycloalkanes larger than cyclohexane for clarification of the reaction mechanism along with the catalytic action of S04/Zr02. 

When no reforming process is carried out in the pyrolysis of PP, 90.50% of the gasoline fraction in the products is olefin, and the yield fractions of isomerized paraffins, cycloalkanes and aromatics are very low. The gasoline has a RON of no more than 80 and is very unstable [99]. However, after reforming and fractionation [100], the results improved significantly, as shown in Table 28.11. Two kinds of molecular sieve catalysts were adopted for the process. 

For some time the main emphasis of Friedel-Crafts reactions was chiefly on aromatic compounds. The development of aliphatic Friedel-Crafts chemistry was of minor importance until World War 2, when isomerization of alkanes and cycloalkanes, preparation of high-octane aviation gasoline and synthetic rubber, and polymerization of alkenes achieved considerable importance these contributed to the growth of aliphatic Friedel-Crafts chemistry. 

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