Alkanes substituents

Similar to the imidazolium ILs, very low solubility of the ammonium ILs was observed in alkanes. Eor example, the solubility of butyl(2-hydroxyethyl) dimethylammonium bromide, [(Ci)2C4HOC2N]Br, exhibited a simple eutectic system with immiscibility in the liquid phase in the IL mole fraction range from XjL = 0.02 to 0.70 [53] the other ammonium salt, (benzyl)dimethyl-alkylammonium nitrate, [Be(Ci)2C N] [NOJ showed very small solubility in the liquid phase in hexadecane and it was slightly better in hexane (immiscibility from XjL = 10 to 0.90) [99] for the ammonium salt with an alkane substituent only, didecyldimethylammonium nitrate, [(Cio)2(Q)2N][N03], the solubility in the liquid phase was better in hexane (immiscibility from XjL = 10 to 0.50) than in hexadecane, where the immiscibility was observed in the whole IL mole frachon [100]. In all systems with imidazolium and ammonium salts, an increase in the alkyl chain length of the alkane (solvent) resulted in a decrease of solubility. 

Alkane Substituent Group(s) Derived from Alkane ... 

A severe limitation is related to the limited number of functional groups, which can be introduced in the cw-position of the alkane substituent due to unwanted side reactions. An alternative approach rehes on the forma-... 

Olefinic CH stretching frequencies occur at 3130-2980 cm" In trialkyl substituted ethylenes, the lone =CH stretch band can be seen in the region 3050-2990 cm , but non-alkane substituents can raise the wavenumbers (trichloroethylene, 3083 cm" ). ... 

The out-of-phase =CH2 stretch vibrations in vinyls (monosubstituted eth-ylenes) and vinylidenes (1,1-disubstituted ethylenes) give rise to a band at 3100-3070 cm" in hydrocarbons, and slightly higher for non alkane substituents. This band is well separated from CH3 bands below 3000 cm ... 

The in-phase =CH2 stretching vibration band is often obscured by alkane substituent absorption. When the alkane substituent groups in 1,1-dialkyl ethylenes have no CH3 group, the in-phase =CH2 stretch band can be seen... 

Fig. 7.2. General IR spectra expected for ethylenes with alkane substituents.

Examples of these infrared bands are seen in Fig. 8.7. The first two rows of spectra illustrate benzene rings with alkane substituents. For these, the adjacent hydrogen wag bands tend to increase in frequency somewhat as the a carbon of the substituent is more highly substituted. We can note absorptions for toluene at 728 cm ethylbenzene at 745 cm isopropylbenzene at 759 cm and /ert-butylbenzene at 763 cm ... 

For program SIMULA, the values of A, Zj, and corr are stored in tables. There are currently 39 basic carbon chemical shifts and 2479 values of for 150 substituents. Theoretically there are many more different values of Z for these substituents (e.g., the program now contains 467 out of a possible 600 for the alkane substituent, but only 39 of the 300 for the cyclopropane substituent), leading to some limitations, but largely in the case of the less common substituents. The tables of VODIK contain 22 basic proton shifts and the values of Zj for 85 substituents. 

Alkane Substituent groups derived from alkane ... 

Saturated hydrocarbons are classified by the parent name alkanes substituent groups derived from them are called alkyl (or alkanyl, see below) groups. The naming system is based on the unbranched members of the homologous series C H2 +1 of which only the first four are designated by trivial names. 

Over the past decade it has been established that for various substituents the i C chemical shift increment is a constitutive property. This applies to many systems e.g. benzenes, alkanes and alkenes. The availability of over 200 allenes, randomly substituted with groups of different nature, enabled us to prove that in the case of allenes the chemical shift increment is a constitutive property too, thus establishing a convenient method for estimating i ( C) values for allenes. 

Write the name of the compound The parent alkane is the last part of the name and is preceded by the names of the substituent groups and their numerical locations (locants) Hyphens separate the locants from the words... 

As numbered on the structural formula the longest continuous chain contains eight car bons and so the compound is named as a derivative of octane Numbering begins at the end nearest the branch and so the ethyl substituent is located at C 4 and the name of the alkane is 4 ethyloctane... 

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... 

Name the compound as a cycloalkyl substituted alkane if the substituent has more carbons than the ring... 

It IS no accident that sections of our chair cyclohexane drawings resemble saw horse projections of staggered conformations of alkanes The same spatial relationships seen m alkanes carry over to substituents on a six membered ring In the structure... 

Substitutive nomenclature of alkyl halides treats the halogen as a halo—(fluoro chloro bromo or lodo ) substituent on an alkane chain The carbon chain is numbered m the direction that gives the substituted carbon the lower number... 

Alkenes resemble alkanes m most of their physical properties The lower molecular weight alkenes through 4 are gases at room temperature and atmospheric pressure The dipole moments of most alkenes are quite small Among the 4 isomers 1 butene cis 2 butene and 2 methylpropene have dipole moments m the 0 3-05 D range trans 2 butene has no dipole moment Nevertheless we can learn some things about alkenes by looking at the effect of substituents on dipole moments... 

Substitutive lUPAC nomenclature names epoxides as epoxy derivatives of alkanes According to this system ethylene oxide becomes epoxyethane and propylene oxide becomes 1 2 epoxypropane The prefix epoxy always immediately precedes the alkane ending it is not listed m alphabetical order like other substituents... 

Systematic names for carboxylic acids are derived by counting the number of car bons m the longest continuous chain that includes the carboxyl group and replacing the e ending of the corresponding alkane by oic acid The first three acids m Table 19 1 methanoic (1 carbon) ethanoic (2 carbons) and octadecanoic acid (18 carbons) illus trate this point When substituents are present their locations are identified by number... 

Polyethylene. The crystal structure of this polymer is essentially the same as those of linear alkanes containing 20-40 carbon atoms, and the values of Tjj and AHf j are what would be expected on the basis of an extrapolation from data on the alkanes. Since there are no chain substituents or intermolecular forces other than London forces in polyethylene, we shall compare other polymers to it as a reference substance. 

If an H atom in an alkane R-// is replaced by a substituent X, the C chemical shift 8c in the a-position increases proportionally to the electronegativity of X (-/ effect). In the (1-position, Sc generally also increases, whereas it decreases at the C atom y to the substituent (y-effect, see Section 2.3.4). More remote carbon atoms remain almost uninfluenced (dSc 0). 

It is particularly interesting to consider the influence of the substituents R and Rj in diphenylol alkanes of the type shown in Figure 20.12. Such variations will influence properties because they affect the flexibility of the molecule about the central C-atom, the spatial symmetry of the molecule and also the interchain attraction, the three principal factors determining the physical nature of a high polymer. 

Deep fluorinalion of alkanes, ethers, acid fmlides, esters, alkyl chlorides, most ketones, ketals, orthoesters, and combinations of these functional groups produces principally the perfluonnated analogues (Table 2) Chlorine substituents (or chloro groups) usually survive fluorination... 

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