Substituted benzenes aromatic compounds

Substituents on benzene or benzenoid rings in fused pyridazines, i.e. in cinnolines and phthalazines, usually exhibit reactivity which is similar to that found in the correspondingly substituted fused aromatic compounds, such as naphthalene, and is therefore not discussed here. 

When two nitro-groups are introduced into the benzene ring the chief product is m-dinitrobenzene, which conforms to the following general laws of substitution. For aromatic compounds there are three important typical reactions 1, halogenation 2, nitration, and 3, sulpho-... 

In contrast to this the mechanism of the homolytic substitution of aromatic compounds is by no means clear. This can be demonstrated by two examples. In Walling s book Free Radicals in Solution published in 1957, three different mechanisms for the phenylation of benzene by benzoyl peroxide are discussed (pages 482-487), no definite differentiation based on direct experimental evidence being possible at that time. On the other hand, it was only in 1958, that new products in addition to biphenyl were identified for the decomposition of benzoyl peroxide in benzene solution when DeTar and Long (1958) isolated l, 4, l ,4"-tetrahydro-p-quaterphenyl (8) and 1,4-dihydrobiphenyl (9). 

The pattern of bands in this region shown by various substituted benzene ring compounds is illustrated in Figure 5-26. It can be seen that a distinct pattern is found for each type of aromatic substitution. For example, a monosubstituted benzene derivative shows a series of four maxima beginning at about 1880 cm" The assignments of these frequencies to combination and overtone bands have been given by Kakiuti and Whiffen [ ]. Since for most compounds these are weak bands, a thicker cell or more concentrated solution is used if this region is to be examined carefully. 

Most aromatic chloro and bromo compounds have strong absorptions at 760-395cm" (13.10-25.32pm) and 650-395cm" (15.38-25.32pm) respectively, which is due to a combination of vibrational modes. Monosubstituted benzenes, dihalogen-substituted benzenes, and compounds with electron-donor or methyl substituents in the para position of halobenzenes all exhibit the former band. 

Despite its own valuable synthetic potential, the use of [ C2]acetylene as a starting material for various building blocks is of much higher relevance. Mercury(II)-catalyzed hydration, for example, gives [ C2]acetaldehyde (Figure 8.5, Route 1) The same reaction carried out in the presence of ammonium persulfate furnishes [ 2] acetic acid (Route 2). Trapping of its mono- or dianion with formaldehyde or carbon dioxide affords [2,3- C2]propynol, [2,3- C2]butyne-l,4-diol, [2,3- C2]propiolic acid " and [2,3- C2]acetylenedicarboxylic acid, respectively (Routes 3-6). UV irradiation of a mixture of HBr and [ C2]acetylene produces l,2-dibromo[ C2]ethane (Route 8) . Reduction with chromium(II) chloride followed by a two-step epoxidation of the initially formed [ C2]ethylene converts [ 2]acetylene into [ C2]ethylene oxide (Route 7) . Finally, catalytic homotrimerization or co-trimerization with other alkynes provides [ " C ]benzene or substituted [ " C ]benzenes, respectively, the central starting materials for the vast majority of substituted benzenoid aromatic compounds (Route 9). 

The nitration, sulphonation and Friedel-Crafts acylation of aromatic compounds (e.g. benzene) are typical examples of electrophilic aromatic substitution. 

It is a typically aromatic compound and gives addition and substitution reactions more readily than benzene. Can be reduced to a series of compounds containing 2-10 additional hydrogen atoms (e.g. tetralin, decalin), which are liquids of value as solvents. Exhaustive chlorination gives rise to wax-like compounds. It gives rise to two series of monosubstitution products depending upon... 

In nitration with nitronium salts in sulpholan, nitrobenzene was substituted in the following proportions 8% ortho, 90% meta and 2% paraf under the same conditions benzylidyne trifluoride yielded 8%, 88% and 4% of 0-, m- and p-nitro compound respectively Both of these aromatic compounds were stated to be io -10 times less reactive than benzene. "... 

Dewar and his co-workers, as mentioned above, investigated the reactivities of a number of polycyclic aromatic compounds because such compounds could provide data especially suitable for comparison with theoretical predictions ( 7.2.3). This work was extended to include some compounds related to biphenyl. The results were obtained by successively compounding pairs of results from competitive nitrations to obtain a scale of reactivities relative to that of benzene. Because the compounds studied were very reactive, the concentrations of nitric acid used were relatively small, being o-i8 mol 1 in the comparison of benzene with naphthalene, 5 x io mol 1 when naphthalene and anthanthrene were compared, and 3 x io mol 1 in the experiments with diphenylamine and carbazole. The observed partial rate factors are collected in table 5.3. Use of the competitive method in these experiments makes them of little value as sources of information about the mechanisms of the substitutions which occurred this shortcoming is important because in the experiments fuming nitric acid was used, rather than nitric acid free of nitrous acid, and with the most reactive compounds this leads to a... 

The above definition implies that the reactivity of an aromatic compound depends upon the reaction which is used to measure it, for the rate of reaction of an aromatic compound relative to that for benzene varies from reaction to reaction (table 7.1). However, whilst a compoimd s reactivity can be given no unique value, different substitution reactions do generally set aromatic compoimds in the same sequence of relative reactivities. 

All compounds that contain a benzene ring are aromatic and substituted derivatives of benzene make up the largest class of aromatic compounds Many such compounds are named by attaching the name of the substituent as a prefix to benzene... 

Many aromatic compounds are simply substituted derivatives of benzene and are named accordingly Many others have names based on some other parent aromatic compound... 

Monocyclic Aromatic Compounds. Except for six retained names, all monocyclic substituted aromatic hydrocarbons are named systematically as derivatives of benzene. Moreover, if the substituent introduced into a compound with a retained trivial name is identical with one already present in that compound, the compound is named as a derivative of benzene. These names are retained ... 

Although there are a wide variety of indole ring syntheses (25), most of the more useful examples fall within a small number of groups. Indole syntheses usually start with an aromatic compound, either monosubstituted or ortho-disubstituted. Those which begin with a monosubstituted starting material must at some point effect a substitution of the benzene ring. 

Styrene undergoes many reactions of an unsaturated compound, such as addition, and of an aromatic compound, such as substitution (2,8). It reacts with various oxidising agents to form styrene oxide, ben2aldehyde, benzoic acid, and other oxygenated compounds. It reacts with benzene on an acidic catalyst to form diphenylethane. Further dehydrogenation of styrene to phenylacetylene is unfavorable even at the high temperature of 600°C, but a concentration of about 50 ppm of phenylacetylene is usually seen in the commercial styrene product. 

Thus cumene [98-82-8] (1-methylethylbenzene, 2-phenylpropane, isopropylbenzene), is a substituted aromatic compound ia the benzene (qv),... 

The effect of substituents on electrophilic substitution can be placed on a quantitative basis by use ofpartial rate factors. The reactivity of each position in a substituted aromatic compound can be compared with that of benzene by measuring the overall rate, relative to benzene, and dissecting the total rate by dividing it among the ortho, meta, and para... 

Non-halogenated plastics Polycyclic aromatic compounds Aliphatics Substituted benzenes... 

Perfluoroalkylation of substituted benzenes and heterocyclic substrates has been accomplished through thermolysis of perfluoroalkyl iodides in the presence of the appropriate aromatic compound Isomeric mixtures are often obtained W-Methylpyrrole [143] and furan [148] yield only the a-substituted products (equation 128) Imidazoles are perfluoroalkylated under LTV irradiation [149] (equation 129). 4-Perfluoroalkylimidazoles are obtained regioselectively by SET reactions of an imidazole anion with fluoroalkyl iodides or bromides under mild conditions [150] (equation 130) (for the SET mechanism, see equation 57)... 

Because of Us high polarity and low nucleophilicity, a trifluoroacetic acid medium is usually used for the investigation of such carbocationic processes as solvolysis, protonation of alkenes, skeletal rearrangements, and hydride shifts [22-24] It also has been used for several synthetically useful reachons, such as electrophilic aromatic substitution [25], reductions [26, 27], and oxidations [28] Trifluoroacetic acid is a good medium for the nitration of aromatic compounds Nitration of benzene or toluene with sodium nitrate in trifluoroacetic acid is almost quantitative after 4 h at room temperature [25] Under these conditions, toluene gives the usual mixture of mononitrotoluenes in an o m p ratio of 61 6 2 6 35 8 A trifluoroacetic acid medium can be used for the reduction of acids, ketones, and alcohols with sodium borohydnde [26] or triethylsilane [27] Diary Iketones are smoothly reduced by sodium borohydnde in trifluoroacetic acid to diarylmethanes (equation 13)... 

The scope of electrophilic aromatic substitution is quite large both the aromatic compound and the electrophilic reagent are capable of wide variation. Indeed, it is this breadth of scope that makes electrophilic aromatic substitution so important. Electrophilic aromatic substitution is the method by which substituted derivatives of benzene are prepar ed. We can gain a feeling for these reactions by examining a few typical examples in which benzene is the substrate. These examples are listed in Table 12.1, and each will be discussed in more detail in Sections 12.3 through 12.7. First, however, let us look at the general mechanism of electrophilic aromatic substitution. 

Pyridine lies near one extreme in being far less reactive than benzene toward substitution by electrophilic reagents. In this respect it resembles strongly deactivated aromatic compounds such as nitrobenzene. It is incapable of being acylated or alkylated under Friedel-Crafts conditions, but can be sulfonated at high temperature. Electrophilic substitution in pyridine, when it does occur, takes place at C-3. 

This last result bears also on the mode of conversion of the adduct to the final substitution product. As written in Eq. (10), a hydrogen atom is eliminated from the adduct, but it is more likely that it is abstracted from the adduct by a second radical. In dilute solutions of the radical-producing species, this second radical may be the adduct itself, as in Eq. (12) but when more concentrated solutions of dibenzoyl peroxide are employed, the hydrogen atom is removed by a benzoyloxy radical, for in the arylation of deuterated aromatic compounds the deuterium lost from the aromatic nucleus appears as deuterated benzoic acid, Eq. (13).The over-all reaction for the phenylation of benzene by dibenzoyl peroxide may therefore be written as in Eq, (14). 

In order to achieve high yields, the reaction usually is conducted by application of high pressure. For laboratory use, the need for high-pressure equipment, together with the toxicity of carbon monoxide, makes that reaction less practicable. The scope of that reaction is limited to benzene, alkyl substituted and certain other electron-rich aromatic compounds. With mono-substituted benzenes, thepara-for-mylated product is formed preferentially. Super-acidic catalysts have been developed, for example generated from trifluoromethanesulfonic acid, hydrogen fluoride and boron trifluoride the application of elevated pressure is then not necessary. 

The reaction of ozone with an aromatic compound is considerably slower than the reaction with an alkene. Complete ozonolysis of one mole of benzene with workup under non-oxidative conditions will yield three moles of glyoxal. The selective ozonolysis of particular bonds in appropriate aromatic compounds is used in organic synthesis, for example in the synthesis of a substituted biphenyl 8 from phenanthrene 7 ... 

The reaction of electron-rich aromatic compounds with yV,A -dimethylformamide 2 and phosphorus oxychloride to yield an aromatic aldehyde—e.g. 3 from the substituted benzene 1—is called the Vilsmeier reaction or sometimes the Vilsmeier-Haack reaction. It belongs to a class of formylation reactions that are each of limited scope (see also Gattermann reaction). 

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. 

---