Alkane Functional Groups

Table 2.1 Alkane C-H stretching vibrations for alkane functional groups as pan of a residual saturated hydrocarbon portion of the molecule (attached to a carbon atom)...

Chemical reactivity and functional group transformations involving the preparation of alkyl halides from alcohols and from alkanes are the mam themes of this chapter Although the conversions of an alcohol or an alkane to an alkyl halide are both classi tied as substitutions they proceed by very different mechanisms... 

The properties that make polyethylene so useful come from its alkane like struc ture Except for the ends of the chain which make up only a tiny portion of the mole cule polyethylene has no functional groups so is almost completely inert to most sub stances with which it comes m contact... 

Ethers are named m substitutive lUPAC nomenclature as alkoxy derivatives of alkanes Functional class lUPAC names of ethers are derived by listing the two alkyl groups m the general structure ROR m alphabetical order as separate words and then adding the word ether at the end When both alkyl groups are the same the prefix di precedes the name of the alkyl group... 

In general, hydroboration—protonolysis is a stereoselective noncatalytic method of cis-hydrogenation providing access to alkanes, alkenes, dienes, and enynes from olefinic and acetylenic precursors (108,212). Procedures for the protonolysis of alkenylboranes containing acid-sensitive functional groups under neutral or basic conditions have been developed (213,214). 

Other immobilization methods are based on chemical and physical binding to soHd supports, eg, polysaccharides, polymers, glass, and other chemically and physically stable materials, which are usually modified with functional groups such as amine, carboxy, epoxy, phenyl, or alkane to enable covalent coupling to amino acid side chains on the enzyme surface. These supports may be macroporous, with pore diameters in the range 30—300 nm, to facihtate accommodation of enzyme within a support particle. Ionic and nonionic adsorption to macroporous supports is a gentle, simple, and often efficient method. Use of powdered enzyme, or enzyme precipitated on inert supports, may be adequate for use in nonaqueous media. Entrapment in polysaccharide/polymer gels is used for both cells and isolated enzymes. 

Just as the alkanes and alkenes had general formulas, the carbon derivatives all have general formulas. The hydrocarbon backbone provides a portion of the general formula, and the functional group provides the other part. In each case, the hydrocarbon derivative is represented by the formula R-, and the hydrocarbon backbone has its own specific formula. The term substituted hydrocarbon is another name for hydrocarbon derivative, because the functional group is substituted for one or more hydrogen atoms in the chemical reaction. 

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... 

Sulfides are sulfur analogs of ethers they contain the C—S—C functional group. They are named as alkylthio derivatives of alkanes in substitutive lUPAC nomenclature. The functional class lUPAC nmnes of sulfides are derived in the same manner as those of ethers, but the concluding word is sulfide. 

The traditional view of molecular bonds is that they are due to an increased probability of finding electrons between two nuclei, as compared to a sum of the contributions of the pure atomic orbitals. The canonical MOs are delocalized over the whole molecule and do not readily reflect this. There is, furthermore, little similarity between MOs for systems which by chemical measures should be similar, such as a series of alkanes. The canonical MOs therefore do not reflect the concept of functional groups. 

Constitutional isomerism is not limited to alkanes—it occurs widely throughout organic chemistry. Constitutional isomers may have different carbon skeletons (as in isobutane and butane), different functional groups (as in ethanol and dimethyl ether), or different locations of a functional group along the chain (as in isopropylamine and propylamine). Regardless of the reason for the isomerism, constitutional isomers are always different compounds with different properties, but with the same formula. 

As we cover new functional groups in later chapters, the applicable IUPAC rules of nomenclature will be given. In addition, Appendix A at the back of this book gives an overall view of organic nomenclature and shows how compounds that contain more than one functional group are named. For the present, let s see how to name branched-chain alkanes and learn some general naming rules that are applicable to all compounds. 

Alkanes are a class of saturated hydrocarbons with the general formula C H2n. -2- They contain no functional groups, are relatively inert, and can be either straight-chain (normal) or branched. Alkanes are named by a series of IUPAC rules of nomenclature. Compounds that have the same chemical formula but different structures are called isomers. More specifically, compounds such as butane and isobutane, which differ in their connections between atoms, are called constitutional isomers. 

The IR spectrum of an alkane is fairly uninformative because no functional groups are present and all absorptions are due to C-H and C-C bonds. Alkane C-H bonds show a strong absorption from 2850 to 2960 cm-1, and saturated C—C bonds show a number of bands in the 800 to 1300 cm-1 range. 

Compounds containing the -C=N functional group are called nitriles and undergo some chemistry similar to that of carboxylic acids. Simple open-chain nitriles are named by adding -nitrile as a suffix to the alkane name, with the nitrile carbon numbered Cl. 

The Lead-Off Reaction Addition of HBr to Alkenes Students usually attach great-importance to a text s lead-off reaction because it is the first reaction they see and is discussed in such detail. 1 use the addition of HBr to an alkene as the lead-off to illustrate general principles of organic chemistry for several reasons the reaction is relatively straightforward it involves a common but important functional group no prior knowledge of stereochemistry or kinetics in needed to understand it and, most important, it is a polar reaction. As such, 1 believe that electrophilic addition reactions represent a much more useful and realistic introduction to functional-group chemistry than a lead-off such as radical alkane chlorination. 

Alkanesulfonates are the petrochemically derived sulfur analogs of soaps, which are alkane carboxylates based on renewable resources. The main difference between alkanesulfonates and soaps is, however, that alkanesulfonates consist of a rather complex mixture of homologs with different carbon chain lengths and isomers with an almost statistical distribution of the functional group along the hydrophobic carbon chain (Fig. 1), whereas soap is a mixture of homologs of alkane 1-carboxylates with an even number of carbon atoms. 

The effective carbon number neff is helpful in characterizing surfactants with an inner functional group. Surfactants with isomeric structures can be compared by means of the hydrophobicity index / [69], which indicates the influence of the effective length of the alkane chain on cM ... 

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. ... 

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