Cycloalkanes groups

The mass spectrometric analyses of the saturate fractions are reported in Table VI. These fractions appear to be composed mostly of alkanes and noncondensed cycloalkanes with smaller amounts of condensed cycloalkanes, mainly two- and three-ring systems. However, because of the presence of olefins in these fractions the analyses are only semiquantitative. In fact, an olefin should make a contribution to the cycloalkane group type which has the same molecular weight. That is, a monoolefin will contribute to the cycloalkanes, a diolefin or a cyclic olein will contribute to the bicycloalkanes, etc. However, to determine the extent of these contributions more analytical work is necessary. 

If the alkane moiety contains more carbon atoms than the ring, the alkane moiety becomes the parent system and the cycloalkane group becomes the substituent. For example, the structure in above figure(b) is called 1-cyclohexyloctane and not octylcyclohexane. The numbering is necessary to identify the position of the cycloalkane on the alkane chain. 

Cis and trans can be used to describe the relationships between groups on a cycloalkane. Groups on the same side of a ring (viewed from the top) are also called cis. If the one group is below the ring and the other above they are called trans (see below). 

B. Naming Substituted Alkanes and Cycloalkanes—Group C Substituents Only... 

There are a total of eighteen different hydrocarbon series, of which the most common constituents of crude oil have been presented - the alkanes, cycloalkanes, and the arenes. The more recent classifications of hydrocarbons are based on a division of the hydrocarbons in three main groups alkanes, naphthanes and aromatics, along with the organic compounds containing the non-hydrocarbon atoms of sulphur, nitrogen and oxygen. 

As you can see cycloalkanes are named under the lUPAC system by adding the prefix cyclo to the name of the unbranched alkane with the same number of carbons as the ring Substituent groups are identified m fhe usual way Their posifions are specified by numbering fhe carbon atoms of fhe ring m fhe direction fhaf gives fhe lowesf num ber to fhe subsfifuenfs af fhe firsf pomf of difference... 

A single alkane may have several different names a name may be a common name or it may be a systematic name developed by a well defined set of rules The most widely used system is lUPAC nomencla ture Table 2 6 summarizes the rules for alkanes and cycloalkanes Table 2 7 gives the rules for naming alkyl groups... 

Name the alkyl group and append it as a prefix to the cycloalkane No locant is needed if the com pound IS a monosubstituted cycloalkane It is understood that the alkyl group is attached to C 1... 

Cycloalkane Number of CH2 groups Heat of combustion per CH2 group... 

When a cycloalkane bears two substituents on different carbons—methyl groups for example—these substituents may be on the same or on opposite sides of the ring When substituents are on the same side we say they are cis to each other if they are on oppo site sides they are trans to each other Both terms come from the Latin m which as means on this side and trans means across... 

The name naphthenic acid is derived from the early discovery of monobasic carboxyUc acids in petroleum, with these acids being based on a saturated single-ring stmcture. The low molecular weight naphthenic acids contain alkylated cyclopentane carboxyUc acids, with smaller amounts of cyclohexane derivatives occurring. The carboxyl group is usually attached to a side chain rather than direcdy attached to the cycloalkane. The simplest naphthenic acid is cyclopentane acetic acid [1123-00-8] (1, n = 1). 

The monofluoromethylene group and difluoromethyl group m 1H perfluoro-alkanes and -cycloalkanes are oxidized at the C-H bond to perfluoroalkyl and perfluorocycloalkyl fluorosulfates by anodic oxidation m fluorosulfonic acid [J, 4] Two modifications of the method are used ox idation by fluorosulfonyl peroxide generated pnor to the reaction [J] (equation 2A) and direct electrolysis m the acid [i, 4] (equabons 2B and 3)... 

Cycloalkane properties depend on ring size. Strained molecules, i.e., moleeules with distorted geometries, tend to be more reaetive in ring-breaking ehemieal reaetions. For example, eombustion of a strained eyeloalkane should release more energy per CH2 group than eombustion of an unstrained moleeule. 

Cycloalkanes (ornaphthenes). These are also known as cycloparaffins or saturated alicyclic hydrocarbons." They are quite stable compounds with the general formula with n > 3 for rings without substituent groups. The first two members are... 

Because of their cyclic structures, cycloalkanes have two faces as viewed edge-on, a "top" face and a "bottom" face. As a result, isomerism is possible in substituted cycloalkanes. For example, there are two different 1,2-dimethyl-cyclopropane isomers, one with the two methyl groups on the same face of the ring and one with the methyls on opposite faces (Figure 4.2). Both isomers are stable compounds, and neither can be converted into the other without breaking and reforming chemical bonds. Make molecular models to prove this to yourself. 

The lack of rotation around carbon-carbon double bonds is of more than just theoretical interest it also has chemical consequences. Imagine the situation for a disubstifitted alkene such as 2-butene. Disubstitilted means that two substituents other than hydrogen are bonded to the double-bond carbons.) The two methyl groups in 2-bulene can be either on the same side of the double bond or on opposite sides, a situation similar to that in disubstitutecl cycloalkanes (Section 4.2). 

Petroleum contains hydrocarbons other than the open-chain alkanes considered to this point. These include cycloalkanes in which 3 to 30 CH2 groups are bonded into closed rings. The structures of the two most common hydrocarbons of this type are shown in Figure 22.5 (p. 585). Cyclopentane and cyclohexane, where the bond angles are close to the ideal tetrahedral angle of 109.5°, are stable liquids with boiling points of 49°C and 81°C, respectively. 

The amount of strain in cycloalkanes is shown in Table 4.6, which lists heats of combustion per CH2 group. As can be seen, cycloalkanes larger than 13 membered are as strain-free as cyclohexane. 

TABLE 4.6 Heats of Combustion A/f in the Gas Phase for Cycloalkanes per CHj group... 

It is possible to perform the conversion CH2 C=0 on an alkane, with no functional groups at all, though the most success has been achieved with substrates in which all CH2 groups are equivalent, such as unsubstituted cycloalkanes. One method uses H2O2 and bis(picolinato)iron(II). With this method, cyclohexane was converted with 72% efficiency to give 95% cyelohexanone and 5% cyclohexanol. ... 

RoCek et al. have also measured rate coefficients for a series of cyclo-alkanes, (CH2) (/i = 4 to 14), and find the analogue of kcHj in equation (25) to fluctuate with ring size in a manner corresponding exactly to the enthalpy of combustion of the cycloalkane concerned per methylene group, provided n is greater than five, i.e. there exists a direct correlation between reactivity and thermochemical strain. 

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