Cycloalkanes sources

Cyclopentane and cyclohexane are present m petroleum but as a rule unsubsti tuted cycloalkanes are rarely found m natural sources Compounds that contain rings of various types however are quite abundant... 

In this chapter we explored the three dimensional shapes of alkanes and cycloalkanes The most important point to be taken from the chapter is that a molecule adopts the shape that minimizes its total strain The sources of strain m alkanes and cycloalkanes are... 

The reduction of an aromatic system under controlled conditions is an important source of cycloalkanes. The procedure given here employs a solution of lithium in a mixture of low-boiling amines to accomplish that end and affords a mixture of octalins as product. The mixture may be separated by selective hydroboration (Chapter 4, Section III). 

Automotive gasoline contains 150 or more different chemical compounds and the relative concentrations of the compounds vary considerably, depending on the source of crude oil, refinery process, and product specifications. Typical hydrocarbon constituents are (volume basis) alkanes (4 to 8%), alkenes (2 to 5%), isoalkanes (25 to 40%), cycloalkanes (3 to 7%), cycloalkenes (1 to 4%), and aromatics (20 to 50%). However, these proportions vary greatly. 

Catalytic reforming92-94 of naphthas occurs by way of carbocationic processes that permit skeletal rearrangement of alkanes and cycloalkanes, a conversion not possible in thermal reforming, which takes place via free radicals. Furthermore, dehydrocyclization of alkanes to aromatic hydrocarbons, the most important transformation in catalytic reforming, also involves carbocations and does not occur thermally. In addition to octane enhancement, catalytic reforming is an important source of aromatics (see BTX processing in Section 2.5.2) and hydrogen. It can also yield isobutane to be used in alkylation. 

Crude oil, however, has almost completely replaced coal as a source of aromatics. Crude oil contains several percents of benzene, toluene, and xylenes and their cycloalkane precursors. The conversion efficiency for preparing toluene or xylenes from their precursors is nearly 100%. For benzene this efficiency is slightly lower. Moreover, alkanes are also transformed to aromatics during refining processes, allowing efficient production of simple aromatic compounds. 

Dehydrohalogenation sometimes leads to cyclization which gives cycloalkanes or heterocycles. The fluorinated diester 1 has proved to be a convenient source of polyfluoroalkylated cyclopropanes. Reaction of 1 with aqueous potassium hydroxide gives 2- HA //-hepta-fluorobutyl)cyclopropane-l, 1 -dicarboxylic acid (2) in quantitative yield.120 The diethyl ester 3 ot this acid is obtained in a yield of 87% by the reaction of 1 with sodium ethoxide in anhydrous ethanol.120... 

As well as atmospheric sources, pyrolysis of fluorine-containing polymers, which may occur in engine oil additives, non-stick cookware or incinerated medical equipment (i.e. syringes) and household waste, may also produce TFA. This process may also produce perfluorinated alkanes and cycloalkanes, which have significant GWP, and have estimated tropospheric half-lives of more than 2000 years. Trifluoroacetate may also be produced by metabolism of trifluoromethyl-containing drugs such as Prozac, and anaesthetics including halothane and iso-fluorane [4],... 

Metal nitrene complexes were used in a number of C-H amination reactions (recent reviews [358, 359]). Copper ketiminate complexes react with azides to nitrene complexes, which were isolated [360]. (p-Ketiminate)copper(I) complex 262 (2.5 mol%) serves therefore as an efficient catalyst for the intermolecular C-H amination of alkylarenes, cycloalkanes, or benzaldehydes 260 using adamantyl azide 261 as the nitrogen source ig. 68) [361]. The corresponding adamantyl amines or amides 263 were isolated in 80-93% yield. Copper complex 262 forms initially a dinuclear bridged complex with 261. From this a copper nitrene complex is generated by elimination of nitrogen, which mediates the hydrogen abstraction from 260. 

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... 

McGee also found the cyclopropane/propene ratio to decrease with increasing pressure in the photolysis of cyclobutanone. However, his data indicated that the change is entirely due to an increase in propene formation, while cyclopropane formation is claimed to be independent of pressure. McGee suggested, on the basis of these results, that propene and cyclopropane were not formed from the same excited state. The deuterium content of the olefin, formed in the photolysis of cyclopentanone-2,2,5,5-rf4, also indicates that the hot cycloalkane is not the only source of the CH2 = CH(CH2) 4CH3 product - . 

The principal source of alkanes is petroleum, together witl tl accompanying natural gas. Decay and millions of years of geologicarstresses have transformed the complicated organic compounds that once made up living plants or animals into a mixture of alkanes ranging in size from one carbon to 30 or 40 carbons. Formed along with the alkanes, and particularly abundant in California petroleum, are cycloalkanes (Chap. 9), known to the petroleum industry as naphthenes. 

These cycloalkanes are converted by catalytic reforming into aromatic hydrocarbons, and thus provide one of the major sources of these important compounds (Sec. 12.4). For example ... 

Crude oils can be classified according to the relative amounts of acyclic alkanes, cycloalkanes and combined aromatic hydrocarbons plus NSO compounds present. This classification is represented by the ternary (triangular) plot in Fig. 4.22, and can be seen to distinguish between the main fields of marine and terrestrially sourced oils. The main classes of normal crudes resulting from this classification are ... 

---