Aromatic hydrocarbons substitution reactions

Aromatic hydrocarbons substituted by alkyl groups other than methyl are notorious for their tendency to disproportionate in Friedel-Crafts reactions. This tendency has previously limited the application of the isomerization of para- or ortho-) m ky -benzenes to the corresponding meta compounds. At the lower temperature of the present modification, disproportionation can be minimized. 

Table 6.4 shows the principal photoreactions of aromatic compounds that we discuss in this chapter. Upon irradiation, aromatic compounds, such as benzenes, naphthalenes and some of their heterocyclic analogues, undergo remarkable rearrangements that lead to some non-aromatic highly strained products, such as benzvalene and Dewar benzene (entry 1), which can be isolated under specific conditions. Quantum and chemical reaction yields are usually low however, photochemistry may still represent the most convenient way for their preparation. While bulky ring substituents usually enhance the stability of those products, aromatic hydrocarbons substituted with less sterically demanding substituents exhibit ring isomerization (phototransposition) (entry 2). 

Aromatic hydrocarbons are nonpolar, and are insoluble in water. They commonly undergo reactions like aromatic electrophilic substitution reactions and reduction reactions. 

The Saturated Aliphatic Hydrocarbons.—For the differentiation between the saturated aliphatic and aromatic hydrocarbons, the reactions typical of the benzene nucleus are applied. The paraffin hydrocarbons are inert towards many of the reagents to which the members of the aromatic series respond the most important reaction of the paraffins is substitution by halogens and this reaction is not suitable for qualitative application. The paraffin hydrocarbons usually met are the various fractions from petroleum and in dealing with these products special provision must be made for reaction due to the presence of not inconsiderable quantities of unsaturated products. 

In aromatic carboxylic acids, the carboxylic acid group (CO2H) is an electron-withdrawing moiety (-1, —M effects), hence it reduces the reactivity of the attached aromatic nucleus towards electrophilic substitution. So like aromatic carbonyl compounds (Section 7), aromatic carboxylic acids are more resistant towards sulfonation than the parent aromatic hydrocarbons. The reaction therefore generally requires rather forcing conditions, e.g. the use of a large excess of chlorosulfonic acid at temperatures of more that 120 °C. The reactions of benzoic, cinnamic and phenylacetic acid with chlorosulfonic acid were reported by Suter. ... 

Aromatic hydrocarbons substituted with easily replaceable halide or nitro groups form mercapturic acids as true metabolites. Tbe reaction with glutathione is catalyzed by a glutathione 6 -aryltransferase. 

The free radical mechanism is confirmed by the fact that if a substituted aromatic hydrocarbon is used in this reaction, the incoming group (derived from the diazotate) may not necessarily occupy the position in the benzene ring normally determined by the substituent present—a characteristic of free radical reactions. 

An important property of aromatic hydrocarbons is that they are much more stable and less reactive than other unsaturated compounds Ben zene for example does not react with many of the reagents that react rapidly with alkenes When reaction does take place substitution rather than addition is observed The Kekule formulas for benzene seem mcon sistent with its low reactivity and with the fact that all of the C—C bonds m benzene are the same length (140 pm)... 

Section 12 17 Polycyclic aromatic hydrocarbons undergo the same kind of electrophilic aromatic substitution reactions as benzene... 

The meaning of the word aromaticity has evolved as understanding of the special properties of benzene and other aromatic molecules has deepened. Originally, aromaticity was associated with a special chemical reactivity. The aromatic hydrocarbons were considered to be those unsaturated systems that underwent substitution reactions in preference to addition. Later, the idea of special stability became more important. Benzene can be shown to be much lower in enthalpy than predicted by summation of the normal bond energies for the C=C, C—C, and C—H bonds in the Kekule representation of benzene. Aromaticity is now generally associated with this property of special stability of certain completely conjugated cyclic molecules. A major contribution to the stability of aromatic systems results from the delocalization of electrons in these molecules. 

Unsaturated hydrocarbons undergo a variety of reactions. Experimentally, alkenes and alkynes undergo addition reactions, whereas aromatic molecules, such as benzene, undergo substitution reactions instead. Why ... 

Although many of the aromatic compounds based on benzene have pleasant odors, they are usually toxic, and some are carcinogenic. Volatile aromatic hydrocarbons are highly flammable and burn with a luminous, sooty flame. The effects of molecular size (in simple arenes as well as in substituted aromatics) and of molecular symmetry (e.g., xylene isomers) are noticeable in physical properties [48, p. 212 49, p. 375 50, p. 41]. Since the hybrid bonds of benzene rings are as stable as the single bonds in alkanes, aromatic compounds can participate in chemical reactions without disrupting the ring structure. 

Accordingly, they do not easily add to reagents such as halogens and acids as do alkenes. Aromatic hydrocarbons are susceptible, however, to electrophilic substitution reactions in presence of a catalyst. 

Aromatic hydrocarbons, like paraffin hydrocarbons, react by substitution, but by a different reaction mechanism and under milder conditions. Aromatic compounds react by addition only under severe conditions. For example, electrophilic substitution of benzene using nitric acid produces nitrobenzene under normal conditions, while the addition of hydrogen to benzene occurs in presence of catalyst only under high pressure to... 

C-Nitration does not involve the hydroxyl group but is a reaction with an aliphatic or aromatic hydrocarbon or a substituted derivative to produce such compounds as the nitroparaffins and the nitrotoluenes ... 

ALCOHOL represents a convenient method of converting allyl alcohol to 2-substituted 1-propanols, while a one-pot reaction sequence of alkylation (alkyl lithium) and reduction (lithium—liquid ammonia) provides excellent yields of AROMATIC HYDROCARBONS FROM AROMATIC KETONES AND ALDEHYDES. 

The reaction of arylbromides with amines affords mostly the corresponding aromatic hydrocarbon by using palladium catalysts, but the expected substituted anilines are formed in good yields by using a nickel (II) catalyst. 

The palladium(O) complex undergoes first an oxydative addition of the aryl halide. Then a substitution reaction of the halide anion by the amine occurs at the metal. The resulting amino-complex would lose the imine with simultaneous formation of an hydropalladium. A reductive elimination from this 18-electrons complex would give the aromatic hydrocarbon and regenerate at the same time the initial catalyst. 

If, instead of a palladium catalyst, a nickel catalyst, such as the bipyridylnickel(II) bromide, is used for the arylation of amines (Fig. 7), the reduction of the aryl halide into the corresponding aromatic hydrocarbon is still present for the primary or secondary benzylamines but, the arylation into substituted anilines is the main reaction even most often the only one, for the other types of amines. 

In fused ring systems, the positions are not equivalent and there is usually a preferred orientation even in the unsubstituted hydrocarbon. The preferred positions may often by predicted as for benzene rings. Thus it is possible to draw more canonical forms for the arenium ion when naphthalene is attacked at the a position than when it is attacked at the p position, and the a position is the preferred site of attack,though, as previously mentioned (p. 682), the isomer formed by substitution at the p position is thermodynamically more stable and is the product if the reaction is reversible and equilibrium is reached. Because of the more extensive delocalization of charges in the corresponding arenium ions, naphthalene is more reactive than benzene and substitution is faster at both positions. Similarly, anthracene, phenanthrene, and other fused polycyclic aromatic hydrocarbons are also substituted faster than benzene. 

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