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“rings” the valencies become deflected from their positions, and that the tension thus introduced may be deduced from a comparison of this angle with the angles at which the strained valencies would meet. He regards the amount of deflection as a measure of the stability of the “ring.” The readiness with which ethylene is acted on in comparison with other types of hydrocarbon, for example, is in harmony, he considers, with the circumstance that the greatest distortion must be involved in its formation, as if deflected into parallelism each valency will be drawn out of its position through ½.109° 28′. The values in other cases are calculable from the formula ½(1O9° 28′ - a), where a is the internal angle of the regular polygon contained by sides equal in number to the number of the carbon atoms composing the ring. These values are:—

Trimethylene. Tetramethylene.
½(109° 28′ − 60°) = 24° 44′.  ½(109° 28′ − 90°) = 9° 44′.
Pentamethylene. Hexamethylene.
½(109° 28′ − 108°) = 0° 44′.  ½(109° 28′ − 120°) = −5° 16′.

The general behaviour of the several types of hydrocarbons is certainly in accordance with this conception, and it is a remarkable fact that when benzene is reduced with hydriodic acid, it is converted into a mixture of hexamethylene and methylpentamethylene (cf. W. Markownikov, Ann., 1898, 302, p. 1); and many other cases of the conversion of six-carbon rings into five-carbon rings have been recorded (see below, Decompositions of the Benzene Ring). Similar considerations will apply to rings containing other elements besides carbon. As an illustration it may be pointed out that in the case of the two known types of lactones—the γ-lactones, which contain four carbon atoms and one oxygen atom in the ring, are more readily formed and more stable (less readily hydrolysed) than the δ-lactones, which contain one oxygen and five carbon atoms in the ring. That the number of atoms which can be associated in a ring by single affinities is limited there can be no doubt, but there is not yet sufficient evidence to show where the limit must be placed. Baeyer has suggested that his hypothesis may also be applied to explain the instability of acetylene and its derivatives, and the still greater instability of the polyacetylene compounds.


The ringed structure of benzene, C6H6, was first suggested in 1865 by August Kekulé, who represented the molecule by six CH groups placed at the six angles of a regular hexagon, the sides of which denoted the valencies saturated by adjacent carbon atoms, the fourth valencies of each carbon atom being represented as saturated along alternate sides. This formula, notwithstanding many attempts at both disproving and modifying it, has well stood the test of time; the subject has been the basis of constant discussion, many variations have been proposed, but the original conception of Kekulé remains quite as convenient as any of the newer forms, especially when considering the syntheses and decompositions of the benzene complex. It will be seen, however, that the absolute disposition of the fourth valency may be ignored in a great many cases, and consequently the complex may be adequately represented as a hexagon. This symbol is in general use; it is assumed that at each corner there is a CH group which, however, is not always written in; if a hydrogen atom be substituted by another group, then this group is attached to the corner previously occupied by the displaced hydrogen. The following diagrams illustrate these statements:—

EB1911 Chemistry - Benzene, Oxybenzene.jpg

   Benzene.  Abbreviated. Oxybenzene. Abbreviated.

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, C10H10; by fusing three, the hydrocarbons anthracene and phenanthrene, C14H10; by fusing four, chrysene, C18H12, and possibly pyrene, C16H10; by fusing five, picene, C22H14. 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 fluor-anthene. 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 regarded as formed by the replacement of hydrogen atoms by other elements or radicals in exactly the same manner as Distinctions between aliphatic and aromatic the aliphatic series. Important differences, however, are immediately met with when we consider the methods by which derivatives are obtained. For example: nitric acid and sulphuric 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·COOH, 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·CH2Cl, and benzal chloride, C6H5·CHCl2. 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 into the benzene nucleus gives rise to compounds generically 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 methylamine, 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, C6H5·NH2, 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 Kekulé 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