Synthesis isopentane

We review here a standard synthesis of unpromoted and promoted WZ catalysts, and their physical characteristics as related to their catalytic performance in the isomerization of n-pentane to isopentane. 

Derivatives of 1,2,3-frithiane as well as 1,2-dithiolane are known for their biological activity. Two naturally occurring frithiane derivatives are shown in Table 6. 5-Methylthio-l,2,3-trithiane has been isolated by gas-phase isopentane extraction from the green alga Chara globulares and identified by GC/MS, H-MR and UV spectra. Its synthesis is straightforward. The second natural frithiane... 

Since there are three pentanes, eight possible amyl chlorides, and therefore eight arrangements of the alcohol CsHuOH, the process is not so simple as indicated in the equations above. In the commercial synthesis, normal pentane and isopentane (2-methylbutane) are submitted to chlorination and subsequent hydrolysis. 

This reaction was first reported by Nenitzescu in 1931. It is the formation of an a,p-unsaturated ketone directly by aluminum chloride-promoted acylation of alkenes with acyl halides. Therefore, it is known as the Darzens-Nenitzescu reaction (or Nenitzescu reductive acylation), or Nenitzescu acylation. Under such reaction conditions, Nenitzescu prepared 2-butenyl methyl ketone from acetyl chloride and 1-butene and dimethylacetylcyclohex-ene from acetyl chloride and cyclooctene. However, in the presence of benzene or hexane, the saturated ketones are often resolved, as supported by the preparation of 4-phenyl cyclohexyl methyl ketone from the reaction of cyclohexene and acetyl chloride in benzene, and the synthesis of 3- or 4-methylcyclohexyl methyl ketone by refluxing the mixture of cycloheptene and acetyl chloride in cyclohexane or isopentane. This is probably caused by the intermolecular hydrogen transfer from the solvent. In addition, owing to its intrinsic strain, cyclopropyl group reacts in a manner similar to an oleflnic functionality so that it can be readily acylated. It should be pointed out that under various reaction conditions, the Darzens-Nenitzescu reaction is often complicated by the formation of -halo ketones, 3,)/-enones, or /3-acyloxy ketones. This complication can be overcome by an aluminum chloride-promoted acylation with vinyl mercuric chloride, resulting in a high purity of stereochemistry. ... 

It was found during studies of ammonia synthesis on iron that the incorporation of a condenser downstream of the sample valve in the external circulation loop of the HPLP apparatus (Fig. 7), enabled the system to be run as a flow rather than a batch reactor. This is true for any reaction system where the reactants are more volatile than the products, since the condenser temperature can be adjusted to trap the products almost exclusively, allowing a nearly pure stream of reactants to impinge on the catalyst. In the case of ammonia synthesis, (where, next to the product, nitrogen at a partial pressure of 5 atm was the most condensable species) a slurry of isopentane (— 159.9 °C) was found to be the ideal condenser medium. During a study of rhenium-catalyzed ammonia synthesis the isopentane condenser was switched in periodically to reduce the ammonia partial pressure to below that at which it appeared to poison the catalyst. In this way, the rhenium was able to produce ammonia in excess of the amount usually leading to poisoning. 

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