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HCOCH HCOCH HC CH HC CH CH CH Ocnzenc, Abbrenrt<e.Oxyccnceoe.ebererfeua. ' From the benzene nucleus we can derive other aromatic nuclei, graphically represented by fusing two or more hexagons along common sides. By fusing two nuclei we obtain the formula of naphthalene, C1oH3 ; by fusing three, the hydrocarbons anthracene and phenanthrene, C,4Hlo; by fusing four, chrysene, C13H12, and possibly pyrene, C16H1,,; by fusing five, picene, C22H,4. But it must be here understood that each member of these condensed nuclei need not necessarily be identical in structure; thus the central nuclei in anthracene and phenanthrene differ very considerably from the terminal nuclei (see below, Condensed Nuclei). Other hydrocarbon nuclei generally classed as aromatic in character result from the union of two or more benzene nuclei joined by one or two valencies with polymethylene or oxidized polymethylene rings; instances of such nuclei are indene, hydrindene, fluorene, and fluoranthene. From these nuclei an immense number of derivatives may be obtained, for the hydrogen atoms may be substituted by any of the radicals discussed in the preceding section on the classification of organic compounds. We now proceed to consider the properties, syntheses, decompositions and constitution of the benzene complex. It has already been stated that benzene derivatives may be Dlstiacregarded as formed by the replacement of hydrogen tions atoms by other elements or radicals in exactly the ttphattc same manner as in the aliphatic series. Important and differences, however, are immediately met with aromatic when we consider the methods by which derivatives comare obtained. For example: nitric acid and sulphuric pounds. acid readily react with benzene and its homologues with the production of nitro derivatives and sulphonic acids, while in the aliphatic series these acids exert no substituting action (in the case of the olefines, the latter acid forms an addition product); another distinction is that the benzene complex is more stable towards oxidizing agents. This and other facts connected with the stability of benzenoid compounds are clearly shown when we consider mixed aliphatic-aromatic hydrocarbons, i.e. compounds derived by substituting aliphatic radicals in the benzene nucleus; such a compound is methylbenzene or toluene, C6H5•CH3. This compound is readily oxidized to benzoic acid, C6H5•000H, the aromatic residue being unattacked; nitric and sulphuric acids produce nitro-toluenes, C6H4•CH3•NO2, and toluene sulphonic acids, C6H4•CH3•SO3H; chlorination may result in the formation of derivatives substituted either in the aromatic nucleus or in the side chain; the former substitution occurs most readily, chlor-toluenes, C6H4•CH3•Cl, being formed, while the latter, which needs an elevation in temperature or other auxiliary, yields benzyl chloride, C6H5•CH2C1, and benzal chloride, C6H5•CHC12. In general, the aliphatic residues in such mixed compounds retain the characters of their class, while the aromatic residues retain the properties of benzene. Further differences become apparent when various typical compounds are compared. The introduction of hydroxyl groups Li-Ito the benzene nucleus gives rise to compounds generic-ally named phenols, which, although resembling the aliphatic alcohols in their origin, differ from these substances in their increased chemical activity and acid nature. The phenols more closely resemble the tertiary alcohols, since the hydroxyl group is linked to a carbon atom which is united to other carbon atoms by its remaining three valencies; hence on oxidation they cannot yield the corresponding aldehydes, ketones or acids (see below, Decompositions of the Benzene Ring). The amines also exhibit striking differences: in the aliphatic series these compounds may be directly formed from the alkyl haloids and ammonia, but in the benzene series this reaction is quite impossible unless the haloid atom be weakened by the presence of other substituents, e.g. nitro groups. Moreover, while methyl-amine, dimethylamine, and trimethylamine increase in basicity corresponding to the introduction of successive methyl groups, phenylamine or aniline, diphenylamine, and triphenylamine are in decreasing order of basicity, the salts of diphenylamine being decomposed by water. Mixed aromatic-aliphatic amines, both secondary and tertiary, are also more strongly basic than the pure aromatic amines, and less basic than the true aliphatic compounds; e.g. aniline, C6H5NH2, monomethyl aniline, C6H5•NH•CH3, and dimethyl aniline, C6H5•N(CH3)2, are in increasing order of basicity. These observations may be summarized by saying that the benzene nucleus is more negative in character than the aliphatic residues. Isomerism of Benzene Derivatives.—Although Kekule founded his famous benzene formula in 1865 on the assumptions that the six hydrogen atoms in benzene are equivalent and that the molecule is symmetrical, i.e. that two pairs of hydrogen atoms are symmetrically situated with reference to any specified hydrogen atom, the absolute demonstration of the validity of these assumptions was first given by A. Ladenburg in 1874 (see Ber., 1874, 7, p. 1684; 1875, 8, p. 1666; Theorie der aromatischen Verbindungen, 1876). These results may be graphically represented as follows: numbering the hydrogen atoms in cyclical order from 1 to 6, then the first thesis demands that whichever atom is substituted the same compound results, while the second thesis points out that the pairs 2 and 6, and 3 and 5 are symmetrical with respect to 1, or in other words, the di-substitution derivatives 1.2 and 1.6, and also 1.3 and 1.5 are identical. Therefore three di-derivatives are possible, viz. 1.2 or 1.6, named ortho- (o), 1.3 or 1.5, named meta- (m), and 1.4, named para- compounds (p). In the same way it may be shown that three tri-substitution, three tetra-substitution, one penta-substitution, and one hexa-substitution derivative are possible. Of the tri-substitution derivatives, 1.2.3.-compounds are known as " adjacent " or " vicinal " (v), the 1.2.4 as " asymmetrical " (as), the 1.3.5 as " symmetrical " (s); of the tetra-substitution derivatives, 1.2.3.4-compounds are known as " adjacent," 1.2.3.5 as " asymmetrical," and 1.2.4.5 as " symmetrical." Di-derivatives x x o to p v as s v as s Here we have assumed the substituent groups to be alike; when they are unlike, a greater number of isomers is possible. Thus in the tri-substitution derivatives six isomers, and no more, are possible when two of the substituents are alike; for instance, six diaminobenzoic acids, CsH3(NH2)2COOH, are known; when all are unlike ten isomers are possible; thus, ten oxytoluic acids, C6H3-CH3.OH•COOH, are known. In the case of tetra-substituted compounds, thirty isomers are possible when all the groups are different. The preceding considerations render it comparatively easy to follow the reasoning on which the experimental verification of the above statements is based. The proof is divided into two Equfva- tenceof parts: (1) that four hydrogen atoms are equal, and (2) four hydro. that two pairs of hydrogen atoms are symmetrical with gen atoms. reference to a specified hydrogen atom. In the first thesis, phenol or oxybenzene,C6H 6.OH, inwhich wewill assumethe hydroxyl group to occupy position 1, is converted into brombenzene, which is then converted into benzoic acid, C6H5.000H. From this substance, an oxybenzoic acid (meta-), C6H4.OH•COOH, may be prepared ; and the two other known oxybenzoic acids (ortho- and para-) may be converted into benzoic acid. These three acids yield on heating phenol, identical with the substance started with, and since in the three oxybenzoic acids the hydroxyl groups must occupy positions other than 1, it follows that four hydrogen atoms are equal in value. R. Hubner and A. Petermann (Ann., 1869, 149, p. 129) provided the proof of the equivalence of the atoms 2 and 6 with respect Symmetry to 1. From meta-brombenzoicacid twonitrobrombenzoic ofpa/rsof acids are obtained on direct nitration; elimination of the hydrogen bromine atom and the reduction of the nitro to an amino atoms. group in these two acids results in the formation of the same ortho-aminobenzoic acid. Hence the positions occupied by the nitro groups in the two different nitrobrombenzoic acids must be symmetrical with respect to the carboxyl group. In 1879, Hubner (Ann., 195, p. 4) proved the equivalence of the second pair, viz. 3 and 5, by starting out with ortho-aminobenzoic acid, previously obtained by two different methods. This substance readily yields ortho-oxybenzoic acid or salicylic acid, which on nitration yields two mononitro-oxybenzoic acids. By eliminating the hydroxy groups in these acids the same nitrobenzoic acid is obtained, which yields on reduction an aminobenzoic acid different from the starting-out acid. Therefore there must be another pair of hydrogen atoms, other than 2 and 6, which are symmetrical with respect to 1. The symmetry of the second pair was also established in 1878 by E. Wroblewsky (Ann., 192, p. 196). Orientation of Substituent Groups.—The determination of the relative positions of the substituents in a benzene derivative constitutes an important factor in the general investigation of such compounds. Confining our attention, for the present, to di-substitution products we see that there are three distinct series of compounds to be considered. Generally if any group be replaced by another group, then the second group enters the nucleus in the position occupied by the displaced group; thismeans that if we can definitely orientate three di-derivatives of benzene, then any other compound, which can be obtained from or converted into one of our typical derivatives, may be definitely orientated. Intermolecular transformations—migrations of substituent groups from one carbon atom to another—are of fairly common occurrence among oxy compounds at elevated temperatures. Thus potassium ortho-oxybenzoate is converted into the salt of para-oxybenzoic acid at 2200; the three bromphenols, and also the brombenzenesulphonic acids, yield m-dioxybenzene or resorcin when fused with potash. It is necessary, therefore, to avoid reactions involving such inter-molecular migrations when determining the orientation of aromatic compounds. Such a series of typical compounds are the benzene dicarboxylic acids (phthalic acids), C6H4(000H)2. C. Graebe (Ann., 1869, 149, p. 22) orientated the ortho-compound or phthalic acid from its formation from naphthalene on oxidation; the meta-compound or isophthalic acid is orientated by its production from mesitylene, shown by A. Ladenburg (Ann., 1875, 179, p. 163) to be symmetrical trimethyl benzene; terephthalic acid, the remaining isomer, must therefore be the para-compound. P. Griess (Ber., 1872, 5, p. 192; 1874, 7, p. 1223) orientated the three diaminobenzenes or phenylene diamines by considering their preparation by the elimination of the carboxyl group in the six diaminobenzoic acids. The diaminobenzene resulting from two of these acids is the ortho-compound; from three, the meta-; and from one the para-; this is explained by the following scheme: NH2 NH2 NH, NH, Nil, NH, NH, NH2 NH2 NH Hooc NH2 COON COON , O' NH2 0 N H2 W. Korner (Gazz. Chem. Ital., 4, p. 305) in 1874 orientated the three dibrombenzenes in a somewhat similar manner. Starting with the three isomeric compounds, he found that one gave two tribrombenzenes, another gave three, while the third gave only one. A scheme such as the preceding one shows that the first dibrombenzene must be the ortho-compound, the second the meta-, and the third the para-derivative. Further research in this direction was made by D. E. Noetling (Ber., 1885, 18, p. 2657), who investigated the nitro-, amino-, and oxy-xylenes in their relations to the three xylenes or dimethyl benzenes. The orientation of higher substitution derivatives is determined by considering the di- and tri-substitution compounds into which they can be transformed. Substitution of the Benzene Ring.—As a general rule, homologues and mono-derivatives of benzene react more readily with substituting agents than the parent hydrocarbon; for example, phenol is converted into tribromphenol by the action of bromine water, and into the nitrophenols by dilute nitric acid; similar activity characterizes aniline. Not only does the substituent group modify the readiness with which the derivative is attacked, but also the nature of the product. Starting with a mono-derivative, we have seen that a substituent group may enter in either of three positions to form an ortho-, meta-, or paracompound. Experience has shown that such mono-derivatives as nitro compounds, sulphonic acids, carboxylic acids, aldehydes, and ketones yield as a general rule chiefly the meta-compounds, and this is independent of the nature of the second group introduced; on the other hand, benzene haloids, amino-, homologous-, and hydroxy-benzenes yield principally a mixture of the ortho- and para-compounds. These facts are embodied in the " Rule of Crum Brown and J. Gibson " (Jour. Chem. Soc. 61, p. 367): If the hydrogen compound of the substituent already in the benzene nucleus can be directly oxidized to the corresponding hydroxyl compound, then meta-derivatives predominate on further substitution, if not, then ortho- and para-.derivatives. By further substitution of ortho- and para-diderivatives, in general the same tri-derivative [1.2.4] is formed (Ann., 1878, 192, p. 219); meta-compounds yield [1.3.4] and [1.2.3] tri-derivatives, except in such cases as when both substituent groups are strongly acid, e.g. m-dinitrobenzene, then [1.3.5]-derivatives are obtained. Syntheses of the Benzene Ring.—The characteristic distinctions Tri. derivatives Tetra-derivatives x x x x x COON