Methylcyclopentane reaction

Methylcyclopentane-1,3,5-tnone, reaction with semicarbazide hydrochloride, 47, 84... 

Nevertheless, in another branched reaction, the hydrogenolysis of methylcyclopentane on Pt-AhOs (10% Pt) at 230°C, leading to 2- and 3-methylpentane (n-hexane is not practically formed under the conditions used)... 

The values of the adsorption coefficient of hydrogen for both reactions were practically identical (1.9 and 2.1 atm-1). Here, the selectivity of the branched reactions depends on the partial pressure of methylcyclopentane. This difference may be accounted for by assuming that either the cleavage of the C—C bond of methylcyclopentane in the (3-position and in the 7-position with respect to the methyl group does not take place on the same sites of the surface of platinum (or on the sites of the same activity), or that the mechanism of hydrogenolysis is more complex than that ex-... 

Competition kinetics. Cyclization of the 1-hexenyl radical competes with the reaction with BihSnH to form methylcyclopentane. 

Cyclohexane (C) and methylcyclopentane (M) are isomers with the chemical formula C6H12. The equilibrium constant for the rearrangement C M in solution is 0.140 at 25°C. (a) A solution of 0.0200 mol-L 1 cyclohexane and 0.100 mol-I. 1 methylcyclopentane is prepared. Is the system at equilibrium If not, will it will form more reactants or more products (b) What are the concentrations of cyclohexane and methylcyclohexane at equilibrium (c) If the temperature is raised to 50.°C, the concentration of cyclohexane becomes 0.100 mol-L 1 when equilibrium is reestablished. Calculate the new equilibrium constant, (d) Is the reaction exothermic or endothermic at 25°C Explain your conclusion. 

Bodner and Domin (2000) demonstrated the inability of many university students to interpret abbreviated structural portrayals with some atoms implied, rather than shown. The students were asked to predict the major products of the reaction of bromine with methylcyclopentane portrayed as in Fig. 1.2, and to estimate the ratio of the products if bromine radicals were just as likely to attack one hydrogen atom as another. Most of the 200 students predicted three products, with a relative abundance 3 2 2 (Fig. 1.4). 

A similar reaction occurs with 2-methylcyclopentane-l,3-dione,176 and can be done enantioselectively by using the amino acid L-proline to form an enamine intermediate. The (S)-enantiomer of the product is obtained in high enantiomeric excess.177... 

Reaction of the heterocycle with 2-methylcyclopentane-1,3-dione in the presence of pyridine leads directly to tetracyclic intermediate 20. 5 The first step in this transformation probably consists in formation of the olefin 18 by elimination of dimethylamine. 

Attempts to extend this reaction to the five-membered ring olefins 1-methylcyclopentene and norbomene resulted in 1-methylcyclopentane and methylenecyclopentane for the former and products (43)-(48) for the latter(80) ... 

Methylcyclopentane is a powerful probe molecule for the study of metal surfaces. The product distribution on platinum depends on the following factors particle size 491 reaction conditions 492-494 carbonaceous residues,492,493,495 and the extent of the interface between the metal and the support.492,493,495 The hydrogenolysis rate of methylcyclopentane depends on the hydrogen pressure.496,497 The rate exhibits a maximal value as a function of hydrogen pressure on EuroPt catalysts.498 The hydrogenolysis of methylcyclopentane has also been studied over Pt-Ru bimetallic catalysts.499... 

When the reactions of alkane molecules larger than the butanes or neopentane are studied, and in particular when the molecule is large enough to form a Cs or a Ce ring, the complexity of the reaction pathway is considerably increased and an important feature is the occurrence, in addition to isomerization product, of important amounts of cyclic reaction products, particularly methylcyclopentane, formed by dehydrocycliza-tion this suggests the existence of adsorbed cyclic species. The question is whether the reaction paths for dehydrocyclization and isomerization are related. There is convincing evidence that they are. Skeletal interconversions involving n-hexane, 2- and 3-methylpentane may be represented. 

In work under very mild reaction conditions (<300°C) cyclic C6 products always strongly predominate over cyclic C products. This is kinetic rather than thermodynamic in origin, since at 277°C and starting with a reaction mixture containing 50 Torr hydrogen and 5 Torr n-hcxane, for instance, equilibrium in the formation of methylcyclopentane would yield 1.86 Torr of the latter, in benzene 4.99 Torr, and in cyclohexane 0.59 Torr... 

Remainder of reaction by isomerization Anderson and Shimoyama (30, 135). n-H = n-hexane 2-MP = 2-methylpentane MCP = methylcyclopentane. 

By performing excellent model reactions [144], Grubbs and his co-workers demonstrated direct olefin insertion into an M-C bond. Thus, complex 115 was treated with AlEtCl2 to give complex 116, whose decomposition afforded methylcyclopentane. Under the same conditions, the polymerization of ethylene took place. In this way, the insertion of a-olefins into a Ti-C single bond in a model Ziegler-Natta catalyst system was directly observed (Eq. 9). 

The second termination reaction is alkyl chain end transfer from the active species to aluminium [155]. This termination becomes major one at lower temperatures in the catalyst systems activated by MAO. XH and 13CNMR analysis of the polymer obtained by the cyclopolymerization of 1,5-hexadiene, catalyzed by Cp ZrCl2/MAO, afforded signals due to methylenecyclopentane, cyclopentane, and methylcyclopentane end groups upon acidic hydrolysis, indicating that chain transfer occurs both by /Miydrogen elimination and chain transfer to aluminium in the ratio of 2 8, and the latter process is predominant when the polymerization is carried out at — 25°C [156]. The values of rate constants for Cp2ZrCl2/MAO at 70°C are reported to be kp = 168-1670 (Ms) 1, kfr = 0.021 - 0.81 s 1, and kfr = 0.28 s-1 [155]. 

Hydrogenolysis of 2-methylpentane, hexane, and methylcyclopentane has been also studied on tungsten carbide, WC, a highly absorptive catalyst, at 150-350 °C in a flow reactor [80], These reforming reactions were mainly cracking reactions leading to lower molar mass hydrocarbons. At the highest temperature (350 °C) all the carbon-carbon bonds were broken, and only methane was formed. At lower temperatures (150-200 °C) product molecules contained several carbon atoms. 

Aluminum chloride, used either as a stoichiometric reagent or as a catalyst with gaseous hydrogen chloride, may be used to promote silane reductions of secondary alkyl alcohols that otherwise resist reduction by the action of weaker acids.136 For example, cyclohexanol is not reduced by organosilicon hydrides in the presence of trifluoroacetic acid in dichloromethane, presumably because of the relative instability and difficult formation of the secondary cyclohexyl carbocation. By contrast, treatment of cyclohexanol with an excess of hydrogen chloride gas in the presence of a three-to-four-fold excess of triethylsilane and 1.5 equivalents of aluminum chloride in anhydrous dichloromethane produces 70% of cyclohexane and 7% of methylcyclopentane after a reaction time of 3.5 hours at... 

The decarbonylations, which do not appear to be affected by light, are reasonably selective with aromatic aldehydes, yielding the expected product however, significant amounts of other products are obtained with non-aromatic substrates (e.g. cyclohexane-aldehyde gives methylcyclopentane and small amounts of n-hexane, as well as the expected cyclohexane and cyclohexen-4-al gives both cyclohexene and cyclohexane). Indeed, the unexpected products perhaps provided a major clue to an understanding of the reaction mechanism(s) involved. 

An example of a parallel-reaction network is the decomposition of cyclohexane, which may undergo dehydrogenation to form benzene and isomerization to form methylcyclopentane, as follows ... 

For the enallene 352, it has been observed that the intramolecular [2 + 2] cycloaddition route competes with an also intramolecular ene reaction leading to cis-l-ethy-nyl-2-methylcyclopentane (354) via transition state 353 (Scheme 5.52) [149]. 

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